JP2000290317A - Ammonium-tetraarylborate polymer, its production, and underwater antifouling agent containing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifouling agent which is less toxic to the environment, has a persistent antifouling effect, and exhibits an excellent antifouling properties even against Hydrozoa and Oberia, which agent comprises structural units derived from an ammonium-tetraaryl borate compound. SOLUTION: The ammonium-tetraaryl borate polymer contains borate structural units represented by formula I (wherein R1 to R5 are each H or a lower alkyl) and is obtained by reacting a sodium-tetraaryl borate represented by formula II with a polymer comprising structural units represented by formulae III and IV (wherein the signs are as defined in formula I) in amounts to give 0.1-1 equivalent of the former per equivalent of the latter at 10-60 deg.C for 1-48 hr. The obtained polymer comprises ammonium-tetraaryl borate compound structural units and (meth)acrylic ester structural units in a molar ratio of 1:10 to 10:1 and has, though not particularly limited, a number-average molecular weight of 2,000-500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ammonium-tetraaryl borate polymer, a method for producing the same, and an antifouling agent containing water containing the polymer. More specifically, the present invention prevents aquatic organisms from adhering to bottom antifouling of marine vessels and fishing boats, water conduits, underwater structures, fishing nets for aquaculture and stationary, fishing net accessories such as floats and ropes, and the like. The present invention relates to a novel ammonium-tetraarylborate-based polymer useful for the above, a method for producing the same, and an antifouling agent in water containing the polymer as an active ingredient.

[0002]

[Technical background of the invention] When aquatic organisms attach to and proliferate on the bottom of marine vessels or fishing vessels, the surface roughness of the hull increases,
A problem arises in that the operating speed, fuel efficiency and life of the ship are reduced, and the appearance is impaired. In addition, when aquatic organisms adhere to the surface of an underwater structure such as a water channel, there is a problem that the distribution of seawater or the like is obstructed. In addition, if aquatic organisms adhere to fishing nets and fishing net accessories, clogging of the fishing nets will occur, causing increase in weight, damage to fishing nets and fishing net accessories, and death of farmed fish, which will reduce the efficiency of fishing operations. Invitation and other problems occur.

[0003] In order to solve such problems, conventionally, the bottoms of nautical vessels and fishing vessels, water pipes, underwater structures, fishing nets,
Measures have been taken to prevent aquatic organisms from attaching to fishing net accessories. Of these, heavy metal-based organotin compounds, especially organotin polymers, have excellent antifouling properties and are inexpensive,
It has been widely used until recently. Examples of such an organic tin polymer include a tin polymer type antifouling paint containing a copolymer of tributyltin methacrylate and methyl methacrylate and cuprous oxide (Cu ₂ O).

[0004] However, organotin compounds are highly environmentally toxic, cause marine pollution and the occurrence of malformed fish, and tend to accumulate in living organisms. Use is prohibited except for. Under such circumstances, the development of a non-heavy metal based antifouling agent having low environmental toxicity has been desired.

On the other hand, it has long been known that organoboron compounds have a physiologically active effect. It has also been proposed to utilize some organoboron compounds as antifouling agents. U.S. Pat. No. 3,211,679 describes that a triphenylboronamine-based compound can be used for a ship's antifouling agent, and examples of the amine component include an alkylamine and a substituted pyridine.

In Japanese Patent Publication No. 54-1571, a tetraphenyl borate compound represented by the following general formula is described as an antifouling compound.

[0007]

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(In the above formula, X represents a potassium atom, an ammonium group or a quaternized organic nitrogen-containing group, and the nitrogen-containing group may form a heterocyclic ring containing a nitrogen atom. Further, Japanese Patent Publication No. 62-25710 discloses an ammonium-tetraaryl borate compound or a heterocyclic compound complex represented by the following general formula as an antifouling compound.

[0009]

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(Wherein R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group, R ² represents a halogen atom,
R ³ represents a heterocyclic amine, which represents a lower alkyl group or a lower alkenyl group. Further, Japanese Patent Publication No. 62-22022 discloses a tetraphenylborate derivative represented by the following general formula as an antifouling compound. Have been.

[0011]

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(In the above formula, R represents a lower alkyl group.) However, a method for producing these organoboron compounds at low cost has not been established. In addition, among aquatic organisms, no compound showing antifouling properties against hydro insects and overia has not been obtained. For this reason, there is a strong demand for an economical underwater antifouling agent that is a non-heavy metal type, has low environmental toxicity, has a high antifouling effect, and has excellent antifouling properties against hydro insects and oberia. I was

The present inventors have conducted intensive studies to solve such problems, and as a result, a specific novel ammonium-tetraarylborate compound has excellent antifouling property in water and environmental safety, and can be produced at a low cost. The inventors have found that the present invention is excellent in economical efficiency, and have completed the present invention.

[0014]

SUMMARY OF THE INVENTION The present invention is a non-heavy metal type, has low environmental toxicity, has a high antifouling effect in water, maintains the antifouling effect for a long time, and has an antifouling property against hydro insects and oberia. An object of the present invention is to provide an ammonium-tetraaryl borate compound which is excellent and can be produced at a low cost, and an underwater antifouling agent containing the same.

[0015]

SUMMARY OF THE INVENTION The ammonium-tetraaryl borate polymer of the present invention is characterized by containing at least one structural unit of an ammonium-tetraaryl borate compound represented by the general formula (I).

[0016]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and these are the same as each other. (A) The method for producing a first ammonium tetraaryl borate polymer according to the present invention comprises: (A) a sodium-tetraaryl borate represented by the general formula (a);
(B) reacting with a polymer having a structural unit represented by the general formula (b) and / or (b ') to produce the above-mentioned ammonium-tetraaryl borate polymer;

[0018]

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(Wherein, R ⁵ represents an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group)

[0020]

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[0021]

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(In the formulas (b) and (b '), R ¹ ,
R ² , R ³ and R ⁴ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group, which may be the same or different from each other). Further, the method for producing a second ammonium tetraaryl borate polymer according to the present invention comprises polymerizing the ammonium-tetraaryl borate compound represented by the general formula (c) alone, or And the other unsaturated monomer is polymerized together to produce the ammonium-tetraarylborate-based polymer;

[0023]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and these are the same as each other. Or different). In addition,
The underwater antifouling agent of the present invention is characterized by containing the above-mentioned ammonium-tetraarylborate polymer.

[0025]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. <Ammonium-tetraaryl borate-based polymer> The ammonium-tetraaryl borate-based polymer of the present invention is a polymer having an ammonium-tetraaryl borate compound structural unit represented by the following formula (I).

[0026]

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In the above formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group. They may be the same or different. The lower alkyl group referred to here may be linear or branched and includes those having 1 to 10 carbon atoms, but is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of antifouling properties. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group and the like. Among them, methyl group, ethyl group, n-propyl group, i -Propyl group, n-
Butyl group, i-butyl group, sec-butyl group, tert
It is preferably a group selected from a -butyl group.

As the ammonium-tetraaryl borate polymer of the present invention, any of the following embodiments is suitable. A homopolymer formed by one kind of ammonium-tetraaryl borate compound structural unit represented by the above formula (I), and two or more kinds of ammonium-polymers represented by the above formula (I)
A copolymer formed from a tetraaryl borate compound constituent unit, and one or more ammonium compounds represented by the above formula (I)
A copolymer formed from a tetraaryl borate compound constituent unit and one or more other constituent units.

The ammonium-tetraarylborate-based polymer of the present invention is preferably one or more ammonium-tetraarylborate compound structural units represented by the above formula (I) and one or more other structural units. It is preferably a copolymer with units. As a monomer forming another structural unit forming a copolymer with one or more ammonium-tetraarylborate compound structural units represented by the above formula (I), a monomer represented by the above formula (I) Any other unsaturated monomer that forms a radical polymerizable double bond with the unit can be suitably used, and such another unsaturated monomer is represented by the general formula (II). The unsaturated monomer forming the (meth) acrylic acid ester-based constitutional unit is particularly preferable.

[0030]

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In the general formula (II), R ⁶ represents an atom or group selected from the group consisting of a hydrogen atom and a lower alkyl group, and R ⁷ represents a linear or branched alkyl having 1 to 18 carbon atoms. Represents a group. Examples of the unsaturated monomer which forms the (meth) acrylate-based structural unit represented by the general formula (II) include (meth) acrylate methyl ester, (meth) acrylate butyl ester, (meth) acrylate 2-ethylhexyl acrylate,
(Meth) acrylic acid 2-hydroxyethyl ester,
Lauryl (meth) acrylate, stearyl (meth) acrylate and the like can be suitably used.

The structural units other than the (meth) acrylate structural units represented by the general formula (II) include, for example, styrene monomers such as vinyl toluene and styrene; and maleic anhydrides such as maleic anhydride. Acid ester monomers; itaconic acid ester monomers such as itaconic anhydride; and structural units formed from vinyl acetate, vinylpyridone, vinylpyridine, butadiene, vinyl chloride, vinylidene chloride, and the like.

When the ammonium-tetraaryl borate polymer of the present invention is a copolymer, it is usually a random copolymer. As such an ammonium-tetraaryl borate polymer, specifically,
For example, in the above formula (I), an ammonium-tetraarylborate-based structural unit in which R ^{1 to} R ⁵ are each a group shown in Table 1 below, and in the above formula (II), R ⁶ and R ⁷ are each in the following table. And a copolymer with another unsaturated monomer which is a (meth) acrylate-based structural unit, which is the group shown in 1. The polymer according to the present invention is not limited to the following examples. The polymers in Table 1 below are also referred to in Examples described later.

[0034]

【table 1】

(In the table, H is a hydrogen atom, Me is a methyl group,
4-Me is 4-methyl group, Et is ethyl group, n-Pr is normal propyl group, i-Pr is isopropyl group, n-B
u represents a normal butyl group. In the ammonium-tetraaryl borate polymer of the present invention, the molar ratio of the ammonium tetraaryl borate compound structural unit to the other structural unit such as the (meth) acrylate structural unit is usually 1: 1:
It is desirably about 10 to 10: 1, preferably about 1: 5 to 5: 1.

The number average molecular weight of the ammonium-tetraaryl borate polymer of the present invention is not particularly limited, but is preferably a molecular weight capable of forming a coating film, and is usually from 2,000 to 500. 5,000, preferably 5,000 to 200,000. Such ammonium-tetraarylborate-based polymers can be used, for example, in the form of a coelenterate animal such as a hydro insect or an oberia; It shows an excellent antifouling effect against the adhesion of polychaete; and other aquatic organisms.

Further, these ammonium-tetraaryl borate polymers are dissolved in various organic solvents such as aromatic solvents such as xylene, ketone solvents such as methyl isobutyl ketone, and ester solvents such as ethyl acetate. Even when stored for a long time after dissolution, it is stable without phase separation or the like. As described above, the ammonium-tetraaryl borate polymer of the present invention has an antifouling property for preventing adhesion to various kinds of aquatic organisms, and can be stably handled as a solution. It can be used well as an active ingredient of an underwater antifouling agent such as a pesticide, an underwater antifouling paint, and a fishing net antifouling agent.
Excellent workability for imparting antifouling properties such as impregnation. <Method for Producing Ammonium-Tetraarylborate-Based Polymer> Such an ammonium-tetraarylborate-based polymer can be prepared by, as a first method, (A) sodium-tetraarylborate represented by the general formula (a): And (B) a polymer having a structural unit represented by formula (b) or (b ').

[0038]

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(Wherein, R ⁵ represents an atom or group selected from the group consisting of a hydrogen atom and a lower alkyl group)

[0040]

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[0041]

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(In the formulas (b) and (b '), R ¹ ,
R ² , R ³ and R ⁴ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group, which may be the same or different from each other). The polymer (B) having the structural unit represented by the general formula (b) or (b ′) preferably further has a structural unit represented by the general formula (II).

[0043]

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(Wherein, R ⁶ represents an atom or group selected from the group consisting of a hydrogen atom and a lower alkyl group;
R ⁷ represents a linear or branched alkyl group having 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms). More specifically, the ammonium-tetraaryl borate-based polymer is represented by (A) the sodium tetraaryl borate represented by the above-mentioned general formula (a) and (B) the above-mentioned general formula (b) A polymer having a structural unit and / or a structural unit represented by the above general formula (b ′) may be used, for example, by adding (A) sodium tetraaryl to one equivalent of an amino group in the polymer (B). The borate (a) is used in an amount of 0.1 to 1 equivalent at a temperature of 10 to 60 ° C.
It can be manufactured by mixing and stirring under normal pressure for about 48 hours. In such a reaction, an organic solvent such as tetrahydrofuran, toluene, or dimethylformamide may be used. Further, a polymer (B) having a structural unit represented by the above general formula (b) or (b ′)
May have a structural unit formed from another unsaturated monomer.

The sodium-tetraarylborate represented by the general formula (a) used in this production method is not particularly limited, but can be produced, for example, as follows. That is, a 4 mole ratio or an excess of an arylmagnesium halide represented by the following formula (i) and a 4 mole ratio or an excess of an aryllithium represented by the following formula (ii): A solution obtained by diluting a diethylether complex of boron trifluoride in a molar ratio as it is or a solution diluted with a solvent such as toluene is added dropwise to the solution under stirring and cooled, and the mixture is allowed to react under reflux conditions for about 1 hour.

[0046]

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(Wherein X represents a halogen atom, and R ⁵ is the same as described above)

[0048]

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Next, while cooling and stirring the reaction solution,
An excess amount of an aqueous solution of salt, sodium carbonate, sodium hydroxide or the like is added dropwise. After completion of the reaction, the organic layer separated into an upper layer is separated and the solvent is distilled off, whereby white crystals are obtained. After washing with a non-polar solvent such as toluene and drying,
The sodium tetraaryl borate represented by the above formula (a) is obtained as white crystals.

Specific examples of such sodium tetraaryl borates represented by the above formula (a) include, for example, sodium tetraphenyl borate, sodium tetra 4-methylphenyl borate, sodium tetra 3-methylphenyl borate , Sodium tetra 2-methylphenyl borate, sodium tetra 4-ethylphenyl borate, sodium tetra 3-ethylphenyl borate, sodium tetra 2-ethylphenyl borate, sodium tetra 4-n-propylphenyl borate, sodium tetra 3-n-propyl Phenyl borate, sodium tetra 2-n-propyl phenyl borate, sodium tetra 4-i-propyl phenyl borate, sodium tetra 3-i-propyl phenyl borate, sodium tetra 2-i Such as propyl phenyl borate and the like.

Specific examples of the monomer having an amino group which forms the structural unit represented by the above formula (b) include (meth) acrylic acid N, N-dimethylaminoethyl ester and (meth) acrylic acid. Monomethylaminoethyl acrylate, aminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, monomethylaminoethyl (meth) acrylate, N, N-di (meth) acrylate -Propylaminoethyl ester, (meth) acrylic acid N,
Examples thereof include N-di-i-propylaminoethyl ester and N, N-di-n-butylaminoethyl (meth) acrylate.

Further, as the ammonium chloride-containing monomers forming the structural unit represented by the above formula (b ′), specifically, for example, ((2 meth) acryloyloxyethyl) trimethylammonium chloride, ( (2 (meth) acryloyloxyethyl) triethylammonium chloride, ((2meth) acryloyloxyethyl) tripropylammonium chloride, ((2meth) acryloyloxyethyl) tributylammonium chloride and the like can be mentioned.

A specific example of such a first production method is as follows.
This will be exemplified in Example 1 described later. In addition, such an ammonium-tetraaryl borate polymer can be produced by the following method as a second method. That is, it can be produced by polymerizing the ammonium-tetraaryl borate compound represented by the general formula (c) alone, or by polymerizing the ammonium-tetraaryl borate compound and another unsaturated monomer together. And preferably represented by the general formula (c)
Can be produced by copolymerizing an ammonium tetratetraborate compound represented by the formula (I) with an unsaturated monomer (meth) acrylate-based monomer represented by the general formula (d).

[0054]

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[0055]

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(In the equations (c) and (d),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group, which may be the same or different. , R ⁶ represents an atom or group selected from the group consisting of hydrogen atoms and lower alkyl groups, R ⁷
Represents a linear or branched alkyl group having 1 to 18 carbon atoms).

A specific example of such a second production method is as follows.
This will be exemplified in a second embodiment described later. <Underwater antifouling agent> Examples of the underwater antifouling agent according to the present invention include an underwater pest control agent, an underwater antifouling paint, and a fishing net antifouling treatment agent. It contains a polymer as an active ingredient.

Such underwater antifouling agents are used in water, such as the bottoms of oceangoing vessels and fishing boats, headraces, underwater structures, fishing nets for aquaculture and stationary, fishing net attachments such as floats and ropes, and the like. It can be effectively used to prevent the attachment of aquatic organisms to underwater structures such as underwater structures such as ships, aquaculture nets, stationary nets, excavators for offshore oilfields, offshore bases, buoys, waterway facilities for power plants, bridges, etc. The method can be applied to an object requiring biological antifouling by a method such as coating or coating.

The underwater antifouling agent of the present invention may contain the ammonium-tetraarylborate-based polymer in an effective amount so as to exhibit an antifouling effect, and the content is not particularly limited. This ammonium-tetraaryl borate polymer may be used as it is. For example, when the underwater antifouling agent of the present invention is an underwater antifouling paint, an ammonium-tetralyl borate polymer is used.
Usually, it is desirable to contain it in an amount of 10 to 90% by weight, preferably 20 to 70% by weight.

In the present invention, the above-mentioned ammonium-tetraarylborate-based polymer of the present invention can be used as it is as an antifouling agent in water. However, depending on the purpose and object, paints, solutions, emulsions or pellets may be used. It is formulated into appropriate dosage forms in a conventional manner, and the formulation is converted into submersible water, such as ships, aquaculture nets, stationary nets, offshore oilfield excavators and bases, buoys, power plant waterway facilities, bridges and other structures. It may be used by a method such as application to an object requiring antifouling of living organisms.

The underwater antifouling agent of the present invention has a sufficient antifouling property even if only the above-mentioned ammonium-tetraarylborate polymer is used. The known antifouling agent can be blended if desired. Such other antifouling agents include zinc dimethyldithiocarbamate, 2
-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl-N'-
(3,4-dichlorophenyl) urea, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one,
N- (fluorodichloromethylthio) sulfamide, 2
-Pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy,
N- (2,4,6-trichlorophenyl) maleimide,
2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatolyl sulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, triphenylborane pyridine And the like. These antifouling agents other than the ammonium-tetraarylborate polymer may be used alone or in combination of two or more.

Hereinafter, the case where the underwater antifouling agent is an underwater antifouling paint will be described in more detail. When the underwater antifouling agent is an underwater antifouling paint, it is preferably a paint using a resin as a coating film forming component, similarly to a general paint used for underwater use. For the preparation of the underwater antifouling paint of the present invention, for example, an ammonium-tetraaryl borate-based polymer is first converted into an alcohol such as n-butyl alcohol, a ketone such as methyl ethyl ketone, an ester such as ethyl acetate, and the like. Benzene, dissolved in an organic solvent such as aromatics such as xylene, and then a solution containing the thus obtained ammonium-tetraaryl borate polymer, an organic solvent, a surfactant, a resin for coating, a plasticizer, The underwater antifouling paint of the present invention can be prepared by uniformly mixing the paint and auxiliary materials such as auxiliary components. In addition, when the ammonium-tetraaryl borate-based polymer, which is the active ingredient of the antifouling agent in water, is well dissolved in the organic solvent that is the base material of the paint, the ammonium-tetraaryl borate-based polymer is previously dissolved in the organic solvent. The underwater antifouling paint may be prepared by mixing with the paint raw material without dissolving.

Examples of the coating resin include vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl isobutyl ether copolymers, chlorinated rubber resins, chlorinated polyethylene resins, and chlorinated polypropylene resins. , Acrylic resin, styrene-butadiene resin,
Examples include polyester resin, epoxy resin, phenol resin, copper acrylate resin, synthetic rubber, silicone rubber, silicone resin, petroleum resin, oily resin, rosin ester resin, rosin resin, and rosin.

The underwater antifouling paint of the present invention may contain a coloring pigment or a coloring agent, if necessary. Examples of such a coloring pigment or coloring agent include coloring pigments such as titanium white, red iron, carbon, cyan blue, and cyanine green, or talc, barita, and zinc white. Further, in order to adjust the viscosity of the underwater antifouling paint of the present invention, water or an organic solvent can be blended. The kind of the organic solvent used for this purpose is not particularly limited as long as it can dissolve or disperse the above-mentioned resin for coating and other components. Examples of such an organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Alcohols such as ethylene glycol and benzyl alcohol; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene and methylnaphthalene; chloroform, carbon tetrachloride, dichloromethane, chloroethylene, trichlorofluoromethane, dichloro Halogenated hydrocarbons such as difluoromethane; ethers such as ethyl ether, ethylene oxide, dioxane, and tetrahydrofuran; acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone; ethyl acetate, butyl acetate,
Esters such as ethylene glycol acetate; nitriles such as acetonitrile, propionitrile and acrylonitrile; sulfoxides such as dimethyl sulfoxide; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylamine, dimethylamine, triethylamine; Amines such as isobutylamine; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; industrial gasoline such as petroleum ether and solvent naphtha; and paraffins; petroleum fractions such as kerosene and gas oil; No.

In the underwater antifouling agent of the present invention, emulsification,
For the purpose of dispersion, wetting, foaming, spreading and the like, a surfactant can be blended as required. The surfactant is not particularly limited, and examples thereof include the following. (A) Nonionic surfactant: For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester and the like. (B) anionic surfactants: for example, alkyl benzene sulfonate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate and the like. (C) Cationic surfactants: for example, alkylamines such as laurylamine, stearyltrimethylammonium chloride, and alkyldimethylbenzylammonium chloride. (D) Amphoteric surfactants: for example, sulfates of betaine-type compounds.

In the underwater antifouling agent of the present invention, in addition to the above-mentioned components, polyvinyl alcohol (PVA),
Various adjuvants such as carboxymethylcellulose (CMC), arabic gum, polyvinyl acetate, gelatin, casein, and sodium alginate can also be blended.

[0067]

According to the present invention, it is a non-heavy metal type, has a low environmental toxicity, has a high antifouling effect in water and maintains the antifouling effect for a long period of time. Shellfish such as animals, barnacles, mussels, oysters, and cerbras;
Ammonium-tetraarylborate-based polymer which is excellent in antifouling property even against the attachment of aquatic organisms such as tubal polychaete such as Yasuku Kansashi and Ozuma-kigokai and can be produced at low cost, and an underwater antifouling solution containing the same. An agent can be provided.

Further, the antifouling agent in water of the present invention dissolves well in various organic solvents, so that it can be handled as a solution-form preparation, and has an effect of having excellent stability even during long-term storage.

[0069]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. <Test Method> In Examples and Comparative Examples, the evaluation of an underwater antifouling agent as an underwater antifouling paint and a fishing net antifouling treatment agent was as follows.
The test was performed according to the following test method.

Underwater antifouling paint test Shop An antifouling paint prepared as described below is applied to a 300 × 100 × 3.2 mm sandblasted steel sheet coated with a primer and a vinyl tar-based anticorrosive paint to a dry film thickness of 100 μm. Paint with air spray to make a test plate. After drying the test plate for 7 days, the test plate is immersed still in the sea off Tamano City, Okayama Prefecture, and the degree of adhesion of the pests in water and slime is evaluated. Water pests include hydro insects,
Obelia, barnacle, sea squirt, serpura, purple mussel,
It refers to underwater pests such as mussels and harborers, and underwater pests such as Aonori and Aosa.

The amount of pests in water is indicated by the ratio of the area of adhesion (adhesion ratio) determined by the following equation.

[0072]

(Equation 1)

The degree of adhesion of the slime is evaluated according to the criteria shown in the following table.

[0074]

[Table 2]

Test of Fishing Net Antifouling Agent Test The fishing net is sufficiently immersed in the fishing net antifouling agent prepared as described later. This fishing net is fixed on a 40 × 80 cm iron frame, dried for one day, and used as a test fishing net. The test fishing net is suspended from a pontoon net of a culture net installed off the coast of Tamano City, Okayama Prefecture, immersed in a still water at a depth of 5 m, and the adherence rate of the underwater pests adhered after a predetermined immersion period is visually evaluated.

[0076]

Example 1 Ammonium-tetraarylborate system
Synthesis of copolymer (first production method) The inside of a dropping funnel having a capacity of 100 ml was replaced with nitrogen gas.
After removing oxygen and moisture in the funnel, sodium-
2.65 g (10 mmol) of tetraphenylborate
And a 1: 1 mixed solvent of tetrahydrofuran and toluene 5
0 ml was introduced and dissolved to prepare a sodium tetraphenylborate solution.

In another 200 ml four-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet, (2-
2.08 g (10 mmol) of (methacryloyloxyethyl) trimethylammonium chloride and 5 ml of DMF were added, and nitrogen gas was flowed from the nitrogen inlet to replace the inside of the flask with nitrogen gas. This was kept at 80 ° C. with stirring. Subsequently, 1.98 g (10 mmol) of methacrylic acid 2-ethylhexyl ester and AI were added to 2 ml of DMF.
A solution in which BN (50 mg) was dissolved was added dropwise from a dropping funnel over 10 minutes at the same temperature under a nitrogen stream. After the completion of the dropwise addition, the viscosity of the mixture rapidly increased, then gradually decreased, and finally a stable homogeneous viscous liquid solution was obtained in 3 hours. Next, after cooling the solution, the sodium tetraphenyl borate solution (10 mmol) previously prepared was added dropwise from the dropping funnel with stirring,
The mixture was reacted by stirring at room temperature for 5 hours. After completion of the reaction, the mixture was washed with water, and the organic solvent was distilled off under reduced pressure. A brown viscous liquid (copolymer: corresponding to No. 1 in Table 1 above)
was gotten. The nonvolatile content was almost the same as the total weight of the charged monomers and tetraphenyl borate.

The number average molecular weight of the obtained copolymer is 100
00. The value of the number average molecular weight was measured by GPC (gel permeation chromatography),
It was determined by conversion using a standard polystyrene calibration curve.

[0079]

Example 2 Ammonium-tetraarylborate system
Synthesis of Copolymer (Second Production Method) In a 50 ml four-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet, (2-methacryloyloxyethyl) ammonium tetraphenylborate (10 mmol) and 5 ml of DMF were added. And the inside of the flask was replaced with nitrogen gas by flowing nitrogen gas from a nitrogen inlet, and the flask was maintained at 80 ° C. while stirring. Here, 1.98 g (10 mmol) of 2-ethylhexyl methacrylate was added to AI.
A solution in which BN (50 mg) was dissolved was added dropwise at the same temperature for 10 minutes under a nitrogen stream.

After completion of the dropping, the viscosity of the mixture rapidly increased, then gradually decreased, and finally became stable in 3 hours, and was a homogeneous viscous liquid solution (copolymer: No. 4 in Table 1 above). Was obtained. Of the obtained copolymer,
The number average molecular weight of the copolymer determined by the GPC method was 9,000.

[0081]

Example 3 Preparation and Evaluation of Underwater Antifouling Paint 30 parts by weight of the copolymer obtained in Example 1 was used in a trade name of Laroflex MP-45 (trade name of vinyl chloride-vinyl isobutyl ether copolymer manufactured by BASF). ) 10 parts by weight, 6 parts by weight of Bengala, 4 parts by weight of zinc dioxide, Aerosil # 20
0 (trade name of ultra-fine anhydrous silica manufactured by Nippon Aerosil Co., Ltd.) 1 part by weight, 2 parts by weight of chlorinated paraffin, 10 parts by weight of rosin, 22 parts by weight of xylene and 15 parts by weight of methyl isobutyl ketone were added in a total of 100 parts by weight. The mixture was tumbled and mixed in a ball mill for 5 hours to obtain a uniform underwater antifouling paint.

The obtained underwater antifouling paint was subjected to an underwater antifouling paint test according to the test method described above. Table 4 shows the results.

[0083]

Examples 4 to 11 Preparation and Evaluation of Underwater Antifouling Paint In Example 3, the copolymer (1) obtained in Example 1 was used.
, Instead of using 30 parts by weight of each of the ammonium-tetraarylborate-based polymers shown in Table 2 below, the components were mixed in the same manner as in Example 3 to prepare an antifouling paint. .

Example 3 of the obtained underwater antifouling paint
An underwater antifouling paint test was conducted in the same manner as in the above. Table 4 shows the results.

[0085]

Comparative Example 1 Preparation and Evaluation of Underwater Antifouling Paint In Example 3, the copolymer (1) obtained in Example 1 was used.
Instead of using, the same components as in Example 3 were used except that 30 parts by weight of triphenylboranepyridine having a structure represented by the following formula was used to prepare an antifouling paint.

[0086]

Embedded image

The obtained underwater antifouling paint was used in Example 3.
An underwater antifouling paint test was conducted in the same manner as in the above. Table 4 shows the results. In addition, in 24 months of immersion in the underwater antifouling paint test,
Adhesion of aquatic pests such as hydroid insects, oberia, barnacles and blue seaweed was confirmed.

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

Example 12 Preparation and Evaluation of Fishing Net Treatment Agent 5 parts by weight of the copolymer (1) obtained in Example 1, 5 parts by weight of rosin, 70 parts by weight of xylene, 5 parts by weight of acrylic resin, polybutene (trade name) : Polybutene 06N, 10 parts by weight by Nippon Resin Co., Ltd. and silicone resin (trade name:
KF-96-100, manufactured by Shin-Etsu Chemical Co., Ltd.) A total of 100 parts by weight of til isobutyl ketone was dispersed and mixed by tumbling and mixing in a ball mill for 5 hours to obtain a homogeneous underwater antifouling paint. . As the acrylic resin, a methyl methacrylate / n-butyl methacrylate (60/40 (molar ratio)) copolymer having a number average molecular weight of 20,000 was used.

[0091] The resulting fishing net treating agent was subjected to a fishing net treating agent test according to the test method described above. Table 5 shows the results.

[0092]

Examples 13 to 20 Preparation and Evaluation of Fishing Net Treatment Agent In Example 12, instead of using the copolymer (1) obtained in Example 1, an ammonium salt shown in Table 5 below was used.
Except that each tetraaryl borate polymer was used in an amount of 5 parts by weight, the components were mixed in the same manner as in Example 12 to prepare a fishing net treating agent.

The obtained fishing net treating agent was prepared in Example 12
A fishing net treating agent test was conducted in the same manner as in the above. Table 6 shows the results.

[0094]

Comparative Example 2 Preparation and evaluation of fishing net treating agent In Example 12, instead of using the copolymer (1) obtained in Example 1, 5 parts by weight of triphenylboranepyridine having a structure represented by the following formula In the same manner as in Example 12, except that was used, each compounding component was mixed to prepare a fishing net treating agent.

[0095]

Embedded image

The obtained fishing net treating agent was prepared in Example 12
A fishing net treating agent test was conducted in the same manner as in the above. Table 5 shows the results.

[0097]

[Table 5]

[0098]

[Table 6]

The underwater antifouling paints and fishing net antifouling agents of the present invention, which are the underwater antifouling agents of the present invention shown in Examples 4 to 21, are stable without separation even after long-term storage. The workability of the antifouling treatment on the steel plate or fishing net was extremely good. In the untreated section and Comparative Example 2 in which the immersion period was 3 months or more, adhesion of aquatic pests such as hydro insects, oberia, barnacles, and blue seaweed was confirmed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08F 230/06 220: 10) F term (Reference) 4H011 AD01 BA01 BB06 BB18 BB19 BC19 DA23 DC10 DD07 DH02 DH19 4J038 CG141 CH031 CH041 CH211 GA16 NA05 PB05 PB07 PC02 PC04 PC08 PC10 4J100 AL03Q AL04Q AL05Q AL08P AL16P BA32P CA01 CA04 JA01 JA21

Claims (9)

[Claims] An ammonium-tetraaryl borate polymer comprising at least one structural unit of an ammonium-tetraaryl borate compound represented by the general formula (I): (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group. May be). 2. It comprises at least one structural unit of an ammonium tetraaryl borate compound represented by the general formula (I) and at least one structural unit of a (meth) acrylate ester represented by the general formula (II). 2. The ammonium-tetraaryl borate polymer according to claim 1; (Wherein, R ⁶ represents an atom or group selected from the group consisting of a hydrogen atom and a lower alkyl group, and R ⁷ represents a linear or branched alkyl group having 1 to 18 carbon atoms). 3. A compound of the formula (I) wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group,
The ammonium-tetraaryl borate polymer according to claim 1 or 2, which is a group selected from the group consisting of a sec-butyl group and a tert-butyl group. 4. A method comprising: (A) a sodium tetraarylborate represented by the general formula (a); and (B) a polymer having a structural unit represented by the general formula (b) and / or (b ′). 4. A method for producing an ammonium tetraaryl borate polymer, comprising reacting to produce the ammonium tetraaryl borate polymer according to any one of claims 1 to 3. ] (In the formula, R ⁵ represents an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group.) Embedded image (In the formulas (b) and (b ′), R ¹ , R ² , R ³ and R ⁴ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group. May be the same or different). (A) a sodium-tetraaryl borate represented by the general formula (a); and (B) a structural unit represented by the general formula (b) and / or (b ′):
The method for producing an ammonium tetraaryl borate polymer according to claim 4, wherein the polymer is reacted with a polymer having the structural unit represented by the general formula (II). 6. The method according to claim 1, wherein the ammonium tetratetraborate compound represented by the general formula (c) is polymerized alone, or the ammonium tetratetraborate compound is polymerized together with another unsaturated monomer. Paragraph
Producing an ammonium-tetraaryl borate polymer according to any one of items 1 to 3,
Method for producing ammonium tetraaryl borate polymer; (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent an atom or a group selected from the group consisting of a hydrogen atom and a lower alkyl group. May be). 7. An unsaturated monomer copolymerized with an ammonium tetraaryl borate compound represented by the above general formula (c) is a (meth) acrylate monomer represented by the following general formula (d): 7. The method for producing an ammonium tetraaryl borate polymer according to claim 6, wherein: (Wherein, R ⁶ represents an atom or group selected from the group consisting of a hydrogen atom and a lower alkyl group, and R ⁷ represents a linear or branched alkyl group having 1 to 18 carbon atoms). 8. An antifouling agent in water containing the ammonium-tetraaryl borate polymer according to any one of claims 1 to 3. 9. The underwater antifouling agent according to claim 8, wherein the underwater antifouling agent is an underwater pest control agent, an underwater antifouling paint or a fishing net antifouling agent.