WO1998033829A1

WO1998033829A1 - Triphenylboron-containing polymer and use thereof

Info

Publication number: WO1998033829A1
Application number: PCT/JP1998/000375
Authority: WO
Inventors: Akira Shimada; Masanori Kohara; Yoshifumi Shibuya
Original assignee: Yoshitomi Fine Chemicals, Ltd.
Priority date: 1997-01-30
Filing date: 1998-01-28
Publication date: 1998-08-06
Also published as: JP2002161115A

Abstract

A homo- or copolymer having repeating units represented by formula (1) or (2) and a weight-average molecular weight of 1,000 to 1,000,000, and an antifouling agent for aquatic foulings which contains the same. The antifouling agent significantly diminishes the adhesion of aquatic foulings and has an excellent antifouling effect. The triphenylboron-containing polymer functions not only as the active ingredient but as a binder. It less influences the environment.

Description

Specification

Trirefrinol-boron-containing polymer and its use

Technical field

TECHNICAL FIELD The present invention relates to a polymer containing triflatil boron and its use, and more particularly to a fishing net antifouling agent for preventing aquatic fouling organisms from attaching to and propagating on fishing nets for aquaculture or stationary use, and a ship bottom Prevent waterborne fouling organisms from adhering to and proliferating on structures such as floats and ropes used in fishing nets, condenser cooling waterways and conduits for nuclear and thermal power plants, port facilities, and submarine bases. The present invention relates to a triphenylpon-containing polymer which is effective as an antifouling agent for water-fouling organisms such as underwater antifouling paints (hereinafter also referred to as a water-fouling biofouling agent) and a biofouling antifouling agent containing the polymer.

Background art

Since the bottom of ships or fishing nets for aquaculture or stationary use are kept in the sea or in freshwater for a long period of time, helminths such as helminths and obelia, shellfish, tubal polychaetes, seaweeds, bryozoans, and mollusks Aquatic organisms such as animals, for example, various aquatic organisms such as fujibo, ascidian, selbra, mussels, mussels, bryozoans, azas, lanterns, and bacteria attach. When these aquatic organisms attach, ships and fishing nets suffer and suffer significant economic losses. For example, if a fishing net fujibo is attached, it blocks the mesh and obstructs the tide flow, and the lack of oxygen in the water causes the suffocation of the cultured fish and the increase in weight when replacing the net deteriorates workability. In the event of a typhoon, the wave resistance is large, which may cause damage to the net. Also, if these organisms attach to the bottom of the ship, the propulsion efficiency of the ship will be reduced and fuel consumption will increase. For these reasons, these aquatic organisms are called aquatic fouling organisms. In order to reduce the economic loss caused by aquatic fouling organisms, much effort and expense are being spent on maintaining the contaminated objects.

In addition, these aquatic fouling organisms may be used in ships, materials used on the sea surface or in seawater, underwater structures, such as underwater structures, underwater structures, etc. Adhesion grows on the area where the water droplets come in contact with it, causing various damages. For example, the attachment of these aquatic fouling organisms to the hull increases water resistance and consumes extra fuel. In addition, the attachment of these aquatic fouling organisms to underwater structures will cause a decline in facility functions. Thus, the economic loss from aquatic fouling organisms is large.

Various studies and proposals have been made to prevent the adhesion of aquatic fouling organisms. It is known that a series of organotin compounds are effective for practical use. Organic tin compounds are generally highly toxic, and careless handling of commodities containing them can be hazardous to handlers and can have a negative impact on the environment. For these reasons, the emergence of antifouling agents that adhere to water, such as low-polluting fishing net antifouling agents and antifouling paints, has come to be desired.

For example, Japanese Unexamined Patent Publication No. Sho 51-10849 discloses an underwater antifouling paint containing a benzothiazole compound as an effective component. — 2 8 4

Japanese Unexamined Patent Publication No. 2775 and Japanese Patent Publication No. 1-11606 disclose various fishing net antifouling agents, antifouling paint compositions, and fishing nets in which a tetraalkylthiuram disulfide compound is combined with other compounds. An antifouling solution is disclosed in Japanese Examined Patent Publication No. Sho 61-50984, which discloses a pollution control agent for marine structures containing 3-isothiazolone compounds as an active ingredient.

0 665, Japanese Patent Publication No. 2-24224, JP-A-53-930, JP-A-5-210804, JP-A-6-1 Japanese Patent Publication No. 0 0405, JP-A-6-1

Japanese Patent Application Laid-Open No. 2004-0808 discloses antifouling paints containing a maleimide compound as an active ingredient. Various antifouling paints containing cuprous oxide, organotin, thiocarbamate and the like have been studied as ship bottom paints.

However, the conventional antifouling agent described above has a weaker effect of preventing adhesion to helminths such as helminths and oberia, shellfish such as mussels and tube-like polychaetes such as Kanzaneko Kanashi. C. It was known that cuprous oxide was effective for shellfish, which did not effectively prevent the attachment of aquatic fouling organisms. Has been confirmed to be effective against such species. However, copper, a heavy metal, is used as a copper-based antifouling agent. there were.

Also, U.S. Pat.No. 3,211,679 describes a triphenylborane-alkylamine complex compound using an alkylamine having 4 to 20 carbon atoms as an effective component. An antifouling paint containing 5% by weight or more is described.

In addition, Japanese Unexamined Patent Application Publication No. Hei 7-291,813 discloses a fishing net antifouling agent containing triphenylpropane monopyridine salt as an active ingredient. A fishing net antifouling agent containing a triphenylphenol-alkylamine added compound as an active ingredient is disclosed in WO 97/27254, a fishing net antifouling agent containing a trifrinyllipone-rosinamine addition compound as an active ingredient. , Respectively.

These boron-containing compounds are very effective, especially against coelenterates such as helminths, shellfishes such as fujibobo, and tubal polychaetes such as kansane kansetsu, which were previously difficult to prevent adhesion. There has been a need for an effective antifouling agent for a long time.

Disclosure of the invention

INDUSTRIAL APPLICABILITY The present invention is effectively used as an antifouling agent for aquatic organisms such as a fishing net antifouling agent and an antifouling paint which exhibit an excellent antifouling effect on aquatic fouling organisms such as a coelenterate, a shellfish, and a tubal polychaete. An object of the present invention is to provide such a novel triphenylboron-containing polymer and its use.

The present inventors have made intensive studies to overcome the above-mentioned drawbacks of the conventional underwater biofouling agent, and to seek a underwater biofouling agent having a long-term effect. We have invented a novel triphenylboron-containing polymer and an antifouling agent for water-borne organisms containing the same, which have a low fear and exhibit an excellent antifouling effect on aquatic fouling organisms. That is, water-fouling organism antifouling agents containing the novel triphenylboron-containing polymer include worms such as worms and obelia, shellfish such as Fujibo, mussels, oysters, and serpula, and kansane kansashi, hinto kanzashi, chinko kanzashi, and suzukigakikai. The present invention has been found to have an excellent antifouling effect against the attachment of tubal polychaete or other aquatic fouling organisms, and has a long-term antifouling effect, leading to the completion of the present invention. The polymer containing triphenylpropane of the present invention has a resin portion capable of forming a coating film within the same molecule by polymerizing a monomer containing a triphenylpropane compound, so that only the active ingredient is used. Rather, it can also function as a binder and has the characteristic of having even less impact on the environment.

That is, the present invention is as follows.

(1) A homopolymer or copolymer having a repeating unit represented by the following formula (1), and having a weight average molecular weight of 100 to 1000 (hereinafter also referred to as arylamine type polymer) ).

(Wherein, R ′, R ² and R ³ are each selected from the group consisting of hydrogen and an alkyl group having 1-4 carbon atoms.)

② Homopolymer or copolymer having a repeating unit represented by the following formula (2) And a polymer having a polymerization average molecular weight of 100 to 1000 (hereinafter also referred to as a vinylamine-type polymer).

(3) A composition containing the triphenyl alcohol-containing polymer described in (1) or (2) above.

[4] An antifouling agent due to a water-adhering substance containing the polymer containing triphenylboron as described in [1] or [2].

漁 A fishing net antifouling agent containing the triphenyl alcohol-containing polymer according to the above ① or ②

(4) An antifouling paint containing the polymer containing triphenyl vinyl as described in (1) or (4).

⑦Furthermore, bis (2-pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-oxide) copper, 2-tert-butylbutylamino-4-cyclopropylamino-1,6-methylthio-1,3,5 —Triazine, cuprous oxide, copper thiocyanate (CuSCN), alkyl acrylate / methyl methacrylate / triptyl tin = methacrylate copolymer, tetraethylthiuram disulphide, dimethyldithiocarbamate zinc Salts, bis (dimethyldithiocarbamoyl) zinc ethylene bisdithiocarbamate, pyridine-triphenylborane, triphenylborane-alkyl (3 to 30 carbon atoms) amine, triphenylborane bite jinamine, mouth dan Copper oxide, Copper hydroxide, Copper naphthenate, Manganese ethylene bisdithio It, zinc ethylenebisdithiocarbamate, N, N-dimethylcyclopentaphenylurea, 4,5-dichloro-2-n-octyl-3-isothiazolone, N- (fluorodichloromethylthio) phthalimid, N, N'-Dimethyl-1-N'-phenyl-1- (N-fluorodichloromethylthio) sulfamide, 3-phenyl-2-butyl 2-phenylbutylcarbamate, Jodomethylparatolylsulfone and 2_ (4-thiazolyl) monobenzimidazole, 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, general formula (3)

(Wherein R ⁴ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms), a tetraalkylthiuram disulfite represented by the general formula (4)

(Wherein, R ⁵ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group, or a halogen-substituted benzyl group; 'And X ² each represent a chlorine atom.) 2,3-Dichloromaleimides represented by the general formula (5)

(In the formula, R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents hydrogen, alkyl group, halogen-substituted alkyl group, cycloalkyl group, phenyl group, halogen, alkoxy group, carbonyl group, alkenyl group or (F) represents at least one member selected from the group consisting of phenols represented by the following formula (1) as an active ingredient:

⑧ 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, general formula (3)

(3)

(Wherein, R ⁵ is hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, Represents a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group or a halogen-substituted benzyl group, and X ′ and X ² each represent a chlorine atom. Mids and general formula (5)

(In the formula, R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents hydrogen, alkyl group, halogen-substituted alkyl group, cycloalkyl group, phenyl group, halogen, alkoxy group, carbonyl group, alkenyl group or (Indicating an aralkyl group) The antifouling agent for fishing net according to the above-mentioned (1), which contains, as an active ingredient, at least one selected from the group consisting of phenols represented by

⑨Furthermore, bis (2-pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-oxoxide) copper, 2—tertiary butylamino-4—cyclopropylamino—6-methylthio-1,3,5— Triazine, cuprous oxide, copper thiocyanate (CuSCN), alkyl niacracrylate methyl methacrylate 'triptyl tin methacrylate copolymer, tetraethylthiuram disulphide, dimethyldithiocarbamate zinc salt Bis (dimethyldithiocarbamoyl) zinc ethylene bisdithiocarbamate, pyridine-triphenylborane, triphenylborane-alkyl (3 to 30 carbon atoms) amine, triphenylborane bite jinamine, Mouth Copper danide, copper hydroxide, copper naphthenate, manganese ethylene bisdithiolate Quetylenebisdithiobenzene, N, N-dimethyldichlorophenylurea, 4,5-dichloro-1-n-octyl-3-isothiazolone, N- (fluorodichloromethylthio) phthalimid, N, N'—Dimethyl-N, One-Hue 2-ru (N-fluorodichloromethylthio) sulfamide, 3 — odo 2 — p-Pinyl butyl carbamate, jodomethyl para tolylsulfone and 2- (4-thiazolyl) benzoimidazole selected from the group consisting of The antifouling paint according to the above-mentioned [1], comprising at least one of the following as an active ingredient:

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows an IR (infrared) spectrum of the polymer obtained in Synthesis Example 1.

Detailed description of the invention

Examples of the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ³ in the general formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and isobutyl. Can be

Among the trifluoroboron-containing polymers of the present invention, an arylamine-type polymer can be synthesized by the method shown in the following formula.

As a repeating unit

Polymer having

As a repeating unit

+ © ㊀

Na OH

Polymer having

(In the formula, each symbol is as defined above.)

That is, it can be obtained by dropping an aqueous solution of amine homopolymer into an aqueous solution of sodium hydroxide adduct of triphenylboron, washing the precipitated insoluble matter with water, and drying. Examples of the amine include arylamine, 2-methylarylamine, 3-methylarylamine, 2,3-dimethylarylamine, 2-ethylarylamine, 3-ethylarylamine, 2-butylarylamine, and the like. Is mentioned.

Further, by reacting a homopolymer of amide with triphenylpropane in an organic solvent such as toluene or quinylene according to the method shown in the following formula, triphenyl, which is the desired arylamine-type polymer, is obtained. A ruborone-containing polymer can be synthesized.

As a repeating unit

Polymer having

As a repeating unit

Polymer having

(In the formula, each symbol is as defined above.) The reaction temperature may be room temperature, but can be varied up to 80 ° C if necessary. The reaction time is from 1 hour to 20 hours.

Instead of the above-described homopolymer of amide, a copolymer of amide can be used, and the content of triphenylpropene in the resulting polymer containing triphenylpine can be adjusted. The copolymer is obtained by polymerizing the aforementioned arylamine derivative and a suitable ethylenically unsaturated monomer.

Examples of the ethylenically unsaturated monomer include ethylene, propylene, butadiene, isoprene, styrene, indene, acrylonitrile, vinyl ethers, acrylic esters, methacrylic esters, and the like.

Next, the vinylamine type polymer can be synthesized by the method shown in the following formula.

H ₂ C = CH

NHCHO

As a repeating unit

Polymer with

As a repeating unit

Polymer having

As a repeating unit

Polymer having

(Where a, b, and n each represent an integer of 1 or more.) That is, N-vinylformamide is used as a monomer to produce a homopolymer, which is then hydrolyzed to obtain a polyvinylamine-based polymer of any composition. Subsequently, by reacting with triphenylboron, it is possible to synthesize a desired vinylamine-type polymer, which is a triphenylphenol-containing polymer.

The reaction temperature may be room temperature, but can be varied up to 80 ° C if necessary. The reaction time is from 1 hour to 20 hours.

A copolymer can be used in place of the above-mentioned homopolymer, and the content of triphenylpropane in the obtained triphenylpolypentene-containing polymer can be adjusted. The copolymer is obtained by polymerizing the above-mentioned N-vinylformamide and a suitable ethylenically unsaturated monomer.

Commercially available triphenylphenol used herein may be used, or it may be produced by reacting boron trifluoride with phenylmagnesium bromide.

The polymerization average molecular weight of the obtained triphenylboron-containing polymer is from 100 to 100,000, and preferably the polymerization average molecular weight is from 300,000 to 500,000. Can be used. .

The thus-obtained triphenylpon-containing polymer of the present invention can be converted into an antifouling agent that adheres to water in water, for example, a fishing net antifouling agent, an antifouling paint (such as a ship bottom antifouling paint) by an ordinary method. it can.

For example, when used as an antifouling agent for fishing nets, a polymer containing triflate boron may be dispersed or dissolved in an organic solvent such as xylene. If necessary, it can be produced by adding other antifouling components and various resins described below. If necessary, an antifouling component dissolution regulator described below and other components can also be added. You.

The compounding amount of the triphenyl alcohol-containing polymer of the present invention is a force which can be arbitrarily changed depending on the application environment of the fishing net antifouling agent. Usually 1 to less than 50% by weight, preferably 5 to 25% by weight. More preferably, it is from 3% by weight to less than 10% by weight.

Examples of resins used in fishing net antifouling agents include rosin resin, acrylic resin, polybutene resin, chlorinated rubber resin, vinyl chloride resin, alkyd resin, coumarone resin, ethylene monoacetate resin, synthetic rubber, silicone resin, etc. Power is not particularly limited to these. These can be used alone or as a mixture. As the organic solvent used in the fishing net antifouling agent, an aromatic organic solvent, a ketone organic solvent, or an aliphatic organic solvent can be used.For example, xylene, toluene, pseudodocene, getylbenzene, Lietylbenzene, mesitylene, sonoleventnaphtha, butanol, isopropanol, methyl isobutyl ketone, hexane and the like. Further, a mixture thereof may be used.

Other known antifouling components that can be added to the fishing net antifouling agent as necessary include the following known antifouling components.

1,3-Dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, general formula (3)

(In the formula, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and among them, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group are preferred.) Do

Specific examples of tetraalkylthiuram disulfides (3) include tetramethyl thiuram disulfides. Ruthiuram disulfide, tetraethylthiuram disulfide, tetraisopropyl thiuram disulfide, tetra-n-butylthiuram disulfide, and the like.

General formula (4)

(Wherein, R ⁵ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group, or a halogen-substituted benzyl group; 'And X ² each represent a chlorine atom) 2,3-dichloromaleimides

Examples of the alkyl group for R ⁵ include a methyl group, an ethyl group, an isopropyl group, a butyl group, a tertiary butyl group, an octyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. Preferred are 18 alkyl groups. Examples of the halogen-substituted alkyl group include a dichloromethyl group, a dichloroethyl group, and a trichloroethyl group. As the cycloalkyl group, a cycloalkyl group such as a cyclohexyl group is preferable. Examples of the alkyl-substituted phenyl group include a dimethylphenyl group, a getylphenyl group, a methylethylphenyl group and the like. Examples of the halogen-substituted phenyl group include a dichlorophenyl group. Examples of the alkyl-substituted benzyl group include a methylbenzyl group, a dimethylbenzyl group, a acetylbenzyl group, and a monomethylbenzyl group. Examples of the halogen-substituted benzyl group include a chlorobenzyl group and a dichlorobenzyl group.

Specific examples of the 2,3-dichloromaleimides (4) include, for example, 2,3-dichloro-1-ethylmaleide, 2,3-dichloro-isopropylmaleide, 2,3-Dichloro-N-n-butylmaleide, 2,3-Dichloro-N-tert-butylmaleide, 2,3-Dichloro-N-n-octylmaleide, 2,3-Dichloro- N-cyclohexylmaleamide, 2,3-dichloro-N-benzylmaleimide, 2,3-dichloro-N— (2-chlorobenzyl) maleide, 2,3-dichloro-N- (4— Benzyl) maleimide, 2, 3-dichloro-1-N—

(2-Methylbenzyl) maleide, 2,3-Dichloro-N- (2,4-dimethylbenzyl) maleide, 2,3-Dichloro-N- (3,4-dimethylbenzyl: maleide, 2,3-Dichloro-1-N-α-methylbenzylmaleide, 2,3-dichloro-1- (2,4-dichlorobenzyl) maleide, 2,3-Dichloro-1- (2-ethyl-6-) Methylphenyl) maleimide, 2,3-dichloro-

(2,6-Dimethylphenyl) maleic acid, 2,3-dichloro-1- (2,6-diethylphenyl) maleic acid, 2,3-dichloroyl- (2,4-diethylphenyl) maleic acid , 2,3-Dichloro Ν (2,4,6-trimethylfur) maleimide.

General formula (5)

(Wherein, R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents hydrogen, alkyl group, halogen-substituted alkyl group, cycloalkyl group, phenyl group, halogen, alkoxy group, carbonyl group, alkenyl group or Phenols represented by aralkyl groups)

Examples of the alkyl group for R ⁶ , R ⁷ and R ⁸ include alkyl groups having 1 to 9 carbon atoms such as methyl group, ethyl group, isopropyl group, butyl group, tertiary butyl group and nonyl group. And the like. Examples of the halogen-substituted alkyl group include a dichloromethyl group, a dichloroethyl group, a trichloroethyl group, and the like. Examples of the cycloalkyl group include cyclohexyl. Halogen includes fluorine, chlorine, bromine and iodine. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. Examples of the alkenyl group include those having 2 to 4 carbon atoms such as a vinyl group, an aryl group and an isopropyl group. As the aralkyl group, the number of carbon atoms such as benzyl group and cumyl group? ~ 9.

Specific examples of the phenols (5) include, for example, nonylphenol, cumylphenol, 4,6-di-tert-butyl-m-cresol, 1-cyclohexyl-1-methylphenol, 2,6-di-tert-butyl Tert-butyl p-cresol, 2-phenylphenol, 2-butyl-6-ethyl-4-monoisopropylphenol, 2-bromo-6-chloro-4, dichloromethylphenol, 2-fluoro-4-phenol-1 Examples thereof include 3-dichloroethylphenol, 3-hydroxy-15-methoxybenzoic acid, and 4-ethoxy-2-vinylphenol.

The weight ratio of the known antifouling component that may be added as required to the triphenylporone-containing polymer of the present invention can be in the range of 1:10 to 10: 1. As a dissolution modifier used in fishing net antifouling agents, a general formula (6)

R ⁹ ~ (S) fR 9 (6)

(In the formula, R ⁹ represents an alkyl group having 1 to 20 carbon atoms, and m represents an integer of 2 to 10).

Examples of the alkyl group for R ⁹ include those having 2 to 19 carbon atoms such as an ethyl group, a propyl group, a tertiary butyl group, a tertiary amyl group, a tertiary nonyl group, a tertiary dodecyl group, and a nonadecyl group. Is preferred.

Specific examples of the dialkyl polysulfides (6) include, for example, Antsulfite, dipropyl tetrasulfite, tertiary butyl disulfide, tertiary butyl tertulsulfide, tertiary amyrte trussulfite, tertiary nonyl pentasulfite, tertiary Grade dodecyl pentasulfite, dinonadecyl tetrasulfide, and the like.

In addition, polybutene, paraffins, and serine having an average molecular weight of 2000-10000 can also be used as an elution modifier.

Examples of the polybutene having an average molecular weight of 200 to 1000 include, for example, LV-5, LV-10, LV-25, LV-50, and LV-10 manufactured by Nippon Oil Co., Ltd. 0, HV—15, HV—35, HV—50, HV—100, HV—300, and the like. Examples of paraffins include liquid paraffin, paraffin wax, and chlorinated paraffin. Examples of petrolatum include white petrolatum and yellow petrolatum. These elution modifiers can be used alone or as a mixture.

The amount of the dissolution modifier in the composition can be arbitrarily changed according to the conditions of use, but is usually 3 to 20% by weight, preferably 5 to 10% by weight.

Other ingredients that can be used in fishing net antifouling agents include silicone oils. Examples of the silicone oil include dimethyl silicone oil, higher fatty acid-modified silicone oil, alkyl-modified silicone oil, and methylphenylsilicone oil.

When used as an antifouling paint such as a paint for ship bottoms, the polymer containing trifluoropropylone of the present invention, a water-soluble or water-insoluble resin, a component generally used for paint, an organic solvent (xylene, methylisobutyl, etc.) Pigments such as ketone and butyl acetate), pigments such as coloring pigments and extenders (such as red iron oxide, titanium oxide and zinc oxide), plasticizers, fillers (such as talc and finely divided silica), pigments, plasticizers and fillers An additive such as a curing accelerator can be blended and mixed and dispersed using a paint conditioner, a homomixer, or the like. Further, if necessary, other antifouling components, the same elution controlling agent as can be used in the fishing net antifouling agent, and other components can also be blended. The blending amount of the triphenylphenol-containing polymer of the present invention can be arbitrarily changed depending on the application environment of the antifouling paint, but is usually from 1% by weight to less than 80% by weight, preferably from 3% by weight to 40% by weight. %, More preferably from 5% to less than 25% by weight. Other antifouling components which may be added to the antifouling paint as needed include bis (2-pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-1oxide) copper, Tertiary butylamino 4 -cyclopropylamino 6 -methylthio-1,3,

5-triazine, cuprous oxide, copper thiocyanate (CuSCN), alkyl acrylate.methyl methacrylate.triptyltin methacrylate copolymer, tetraethylthiuram disulfite, dimethyldithiol Carbamate zinc salt, bis (dimethyldithiocarbamoyl) zinc ethylenebisdithiocarbamate, pyridin-triphenylphenylborane, triphenylborane-alkyl (3 to 30 carbon atoms) Triphenylborane-n-octadecylamine, triphenylborane-n-hexadecylamine, triphenylborane-n-octylamine, etc.) Manganese ethylene bisdithiocarbamate, zinc ethylenebisdithioka Bamates, N, N-dimethyldichlorophenylurea, 4,5-dichloro1-2-n-octyl-3-isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenylyl ( N-Fluorodichloromethylthio) Sulfamide, 3-O 2-D-propynyl butyl carbonate, Jodomethylbara trisulfone, 2- (4-thiazolyl) benzoisomidazole, Other non-tin Known antifouling components such as a system antifouling compound are exemplified.

In particular, bis (2-pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-oxide) copper, cuprous oxide, N, N-dimethyldichlorophenylurea, 4,5-dichloro- 2 — n — tert-butyl 3 — isothiazolone, pyridine-triphenyl-2-borane, triphenylborane-alkyl (3 to 30 carbon atoms) amine (eg, triphenylborane-n-octyldecylamine, triflatil) Borane-n-hexadecylamine, trifenylborane (n-tributylamine, etc.) Borane bite jinamine, tetraethylthiuram disulfide and the like are preferable. Among these, furthermore, pyridin-1 triphenylborane, triphenylborane monoalkyl (having 3 to 30 carbon atoms) amines (for example, tripyridine borane-n-titadecylamine, trifinylborane-n-) Hexadecylamine, triphenylborane-n-octylamine, etc.), triphenylborane-rosinamine, and tetraethylthiuram disulfide are particularly preferred.

The known antifouling components listed above can be used alone or as a mixture. Further, other antifouling components, various resins, dissolution regulators, and other components which may be added as necessary as exemplified in the aforementioned fishing net antifouling agent can also be used.

Other components commonly used in paints, solvents (Kynlen, methylisobutyl ketone, butyl acetate, etc.), pigments (Bengara, titanium oxide, zinc oxide, etc.), plasticizers, fillers (talc, finely divided silica, etc.) Additives such as a curing accelerator can be blended as needed.

The underwater biofouling agent other than the fishing net antifouling agent and the antifouling paint can be prepared in the same manner as the above fishing net antifouling agent and the antifouling paint.

The underwater biofouling agent such as the fishing net antifouling agent and the antifouling paint of the present invention has low toxicity and high safety, and also has a long-term effect on long-term intestinal animals such as helminths and obelia, Fujibo, mussels, oysters, It shows excellent antifouling effects against tubular polychaetes such as shellfish such as Serpula, Kanane Kanzashi, Hito Kanzashi, Jakoku-Kanashi and Zuzumakigokai, and other aquatic pollutants. .

Hereinafter, the present invention will be described in more detail by describing Synthesis Examples, Examples, and Comparative Examples. The present invention is not limited to these.

Synthesis example 1

In a 500 mL four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and thermometer, add sodium hydroxide adduct of triflunilborone (Tokyo Chemical Co., Ltd .; 9% aqueous solution) 275 g was charged and stirring was started. In the system Was heated to 50 ° C, and 25 g of polyallylamine (manufactured by Nitto Boseki Co., Ltd., “PAA-L”: a 20% aqueous solution, molecular weight of about 10,000) was dropped from the dropping funnel over about 30 minutes. did. After completion of the dropwise addition, stirring was continued at the same temperature for 1 hour. The precipitated insolubles were collected by filtration, washed with water, and dried to obtain 24.9 g of a white polymer substance.

Figure 1 shows the IR (infrared) spectrum. From this result, it was confirmed that it was the target product. The weight-average molecular weight measured by gel filtration chromatography (HPLC) was 53,000.

Synthesis example 2

In a 300 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer, under a nitrogen stream, 100 g of trifluorobenzene (Aldrich reagent) and 50 g of xylene were charged. The stirring was started. The temperature was raised to 70 ° C, and a 2: 6: 2 (molar ratio) methyl metaacrylate-butylacrylate acrylate copolymer (50% xylene solution, molecular weight approx. 70,000) 44 g Was added dropwise over about 30 minutes. The mixture was stirred at the same temperature for 3 hours to progress the reaction. The solvent was distilled off under reduced pressure to obtain 30.4 g of a pale yellow sticky polymer substance.

The result of the IR (infrared) spectrum confirmed that the product was the target. The weight-average molecular weight measured by gel filtration chromatography (HPLC) was 110.000.

Synthesis example 3

In a 500 mL four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and thermometer, add sodium hydroxide adduct of triflunilboron (Tokyo Chemical Co., Ltd .; 9% aqueous solution). 75 g was charged and stirring was started. The temperature in the system was set to 20 ° C, and a polymer with a hydrolysis rate of poly N-vinylformamide of 59% (“PVAM” manufactured by Mitsubishi Chemical Corporation: 10% aqueous solution, molecular weight of about 100,000) 81 g Was added dropwise from a dropping funnel over about 30 minutes. After completion of the dropwise addition, stirring was continued at the same temperature for 1 hour. The precipitated insoluble matter was collected by filtration, washed with water and dried to obtain a white polymer substance 29. The result of IR (infrared) spectrum confirmed that it was the target substance. The weight-average molecular weight measured by gel filtration chromatography (HPLC) was 360.000.

Each of the components shown in the following formulation examples or comparative examples was mixed to prepare a fishing net antifouling agent. Polybutene described in the formulation examples or comparative examples indicates LV-50 (trade name) manufactured by Nippon Petrochemical Co., Ltd. Acryl resin (50% xylene liquid) was manufactured by Mitsubishi Rayon Co., Ltd. LR—1 5 5 (trade name) are shown, respectively.

Prescription example 1

• Polymer synthesized according to Synthesis Example 1

• Atyl resin (50% xylene solution) 30% by weight

• 65% by weight xylene

Prescription example 2

• 20% by weight of polymer substance synthesized according to Synthesis Example 2

• Acrylic resin (50% xylene solution) 10% by weight

• Kinren 70% by weight

Prescription example 3

• 20% by weight of polymer substance synthesized according to Synthesis Example 3

• Acrylic resin (50% xylene solution) 10% by weight

• Xylene 0.70% by weight

The formulation of the comparative example is as follows.

Comparative Example 1

• Tetraethyl thiuram disulphide 10% by weight

* Polybutene 5% by weight

• 5% by weight of yellow petrolatum

'' Acrylic resin (50% xylene solution) 20% by weight

• 60% by weight of xylene Comparative Example 2

• Bis (dimethyldithiocarbamoyl) 10% by weight

Zinc ethylenebisdithiocarbamate

• 5% by weight of polybutene

'' 5% by weight liquid paraffin

• Acrylic resin (50% xylene solution) 20% by weight

• 60% by weight of xylene

Effect test of antifouling agent for fishing net>

Test example 1

After each of the fishing net antifouling agents shown in Formulation Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention were dip-coated on Tetron-free knotted nets (1000, 3rd dimension) and air-dried, For 4 months from August 1996, it was kept in the sea at a height of about 15 m below the sea surface near Kebumori, Hokkaido. The status of net fouling was evaluated according to the following criteria, and the results are summarized in Table 1. Most of the infested organisms were worms.

Evaluation criteria for net fouling

Evaluation A: 0% fouled area of fishing net. No attached organisms.

Evaluation B: Fishing net fouled area 0 to 10%. Slight adherent organisms are present, but practically acceptable.

Evaluation C: Fouled area of fishing net 10-50%. There are many attached organisms and can no longer be used as fishing nets. .

Evaluation D: Fishing net fouled area 50% or more. Extremely large amount of organisms attached.

table 1

According to Table 1, the fishing net antifouling agents of Formulation Examples 1 and 2 are superior to Comparative Example 1 and Comparative Example 2 in that no worms or obieria adhere to the fishing nets submerged in the sea for at least 3 months. It turned out to be effective. That is, it was found that the polymer substances synthesized according to Synthesis Examples 1 and 2 of the present invention exhibited an extremely strong, persistent and practical antifouling effect against helminths such as hydrids and obelia. did.

Test example 2

The fishing net antifouling agents shown in Formulation Example 3 of the present invention and Comparative Examples 1 and 2 were each dipped and applied to a knotless net made of Tetopen (1000 Z26, 3rd dimension) and air-dried. For four months from January 1996, the tsunami was maintained at a height of about 15 m below the sea surface near Taneichi Town, Iwate Prefecture. The status of net fouling was evaluated according to the criteria shown in Test Example 1, and the results are summarized in Table 2. Most of the infested organisms were worms. .

Table 2

As shown in Table 2, the fishing net antifouling agent of Formulation Example 3 did not adhere to the fishing nets immersed in the sea for at least three months, and no worms and obelia adhered to it, and was superior to Comparative Examples 1 and 2. It was found to have. In other words, it was found that the polymer substance synthesized according to Synthesis Example 3 of the present invention exhibited an extremely strong, persistent and practical antifouling effect against helminths such as Hydra worms and Oberia.

Test example 3

Each of the fishing net antifouling agents shown in Formulation Examples 1 and 2 and Comparative Example 1 of the present invention was dipped and applied to a polyethylene knotless net (section 6, 400 denier / 60 pieces) and air-dried. For 6 months from April 1996, the marine vessel was maintained at about 1 m below sea level in Tanabe Bay, Wakayama Prefecture. The condition of net fouling was evaluated according to the criteria shown in Test Example 1, and the results are shown in Table 3. Table 3

1 month 2 months 3 months 4 months 5 months 6 months Formula 1 A A A A A B Formula 2 A A A A B B Comparative 1 B C D

Unprocessed net CD After one month to two months, a large number of organisms including Fujibashi Kasane kanashi adhered to Comparative Example 1 and the untreated net. On the other hand, in Formulation Examples 1 and 2, the adhesion of shellfish, tubal polychaete, and other organisms to the inundated nets was observed for at least 4 months.

Test example 4

The fishing net antifouling agents shown in Formulation Example 3 of the present invention, Comparative Example 1 and Comparative Example 2 were each dipped and applied to a polyethylene knotless net (section 6, 400 denier Z 60 pieces) and air-dried. However, for five months from February 1997, it was maintained at a height of about 1 m below sea level in Sukumo Bay, Kochi Prefecture. The status of net fouling was evaluated according to the criteria shown in Test Example 1, and the results are shown in Table 4.

Table 4

After one month to two months, a large number of organisms including Fujiboka Kasane Kansashi adhered to Comparative Example 1, Comparative Example 2, and the untreated net. On the other hand, in Formulation Example 3, no attachment of shellfish, tubal polychaete, and other organisms was observed on the inundated net for 5 months.

The components were mixed and dispersed at the following coating composition ratio to obtain an antifouling paint.

Prescription example 4

Polymer substance synthesized according to Synthesis Example 3 25% by weight

Rosin 8% by weight Tri-cresyl phosphate 2% by weight Bengala 10% by weight Polyamide wax 1% by weight Kinren 54% by weight Formulation example 5

Polymer substance synthesized according to Synthesis Example 3

Triphenylborane-n-octadecylamine

Rosin

Bengala 10% by weight Talc 10% by weight Polyamide wax 1% by weight Kinren 54% by weight Formulation example 6

Polymer material synthesized according to Synthesis Example 3 5% by weight Triphenylphenylborane bite ginamine 8% by weight Rosin 5% by weight Bengala 10% by weight Talc 15% by weight Zinc white 0.10% by weight Polyamide wax 0.5% by weight Xylene 4 6.5% by weight Prescription example 7

Polymer substance synthesized according to synthesis example 1 2 5% by weight Zinc white 10% by weight Tri cresyl phosphate 5% by weight Talc 10% by weight Polyamide wax 1% by weight Xylene 4 9% by weight Formulation example 8

Polymer substance synthesized according to Synthesis Example 2 1 5% by weight triphenylborane-n-dodecylamine

Rosin 5% by weight Zinc flower 10% by weight Talc 10% by weight Bengala 10% by weight Polyamide wax 1% by weight Xylene 4 4% by weight Formulation example 9

5% by weight of the polymer substance synthesized according to Synthesis Example 1 Trifenylborane-rosinamine 5% by weight Rosin 8% by weight Tricresyl phosphate 2% by weight Bengala 10% by weight Zinc white 10% by weight Polyamide Dowax 0.5% by weight Xylene 59.5% by weight Formulation example 10

Polymer substance synthesized according to Synthesis Example 1 10% by weight Polymer substance synthesized according to Synthesis Example 3 10% by weight Triphenylborane-pyridine 5% by weight Zinc white 10% by weight Tricresyl phosphate 3% by weight talc 10% by weight Polyamide wax 1% by weight Kinren 5 1% by weight Formulation example 1 1

5% by weight of the polymer substance synthesized according to Synthesis Example 2 5% by weight of the polymer substance synthesized according to Synthesis Example 3 Trifluorophenylborane n-—8-% by weight octylane Tetraethylthiuram disulfide

Bengala 10% by weight Talc 15% by weight Zinc white 10% by weight Polyamide wax 1% by weight Xylene 4 1% by weight Formulation example 1 2

Polymer substance synthesized according to Synthesis Example 3 20% by weight Tetramethylthiuram disulfide 5% by weight Rosin 5% by weight Tricresyl phosphate 2% by weight Talc 10% by weight Zinc white 5% by weight Polyamide wax 0. 5% by weight Xylene 52.5% by weight Formulation example 1 3

Polymer substance synthesized according to Synthesis Example 3 10% by weight Cuprous oxide 20% by weight Rosin

Tricresyl phosphate 2% by weight Bengala 10% by weight Polyamide wax 1% by weight Xylene 4 9% by weight Formulation example 1 4

Polymer substance synthesized by Synthesis Example 2 20% by weight Tetraethyl thiuram disulfide 10% by weight Talc 10% by weight Zinc white 10% by weight Polyamide wax 1% by weight Xylene 49% by weight Formulation example 15

Polymer substance synthesized according to Synthesis Example 1 10% by weight Tetramethylthiuram disulfide 5% by weight Cuprous oxide 10% by weight Tricresyl phosphate 3% by weight Bengala 10% by weight Talc 10% by weight Zinc flower 10% by weight Polyamide wax 1% by weight Xylene 4 1% by weight Formulation example 1 6

Polymer substance synthesized according to Synthesis Example 3. 20% by weight Trifenyl borane-η-titadecylane 3% by weight Tetraethyl thiuram disulfide 5% by weight Talc 10% by weight Zinc white 10% by weight Silicone oil Nore 3% by weight Polyamide wax 1% by weight Xylene 4 8% by weight <Anti-fouling paint effect test>

Test example 5

The antifouling paint obtained in Formulation Examples 4 to 16 above was applied twice on a mild steel sheet of 200 mm x 400 mm x 2.3 mm, which was previously primed with antifouling paint, and was sufficiently applied at room temperature. After drying, it can be immersed in the sea at a depth of 1.5 meters and evaluated by measuring the occupied area of attached organisms after 3, 6, 9, and 12 months.

Industrial applicability

The antifouling agent that adheres to water in water, such as an antifouling agent for fishing nets and antifouling paint for ship bottoms, containing the polymer containing triphenylpropane of the present invention has a low risk of environmental pollution, and also has a low risk of coelenterates, shellfish, and tubing. It shows an excellent antifouling effect against aquatic fouling organisms such as polychaetes. Therefore, by using a composition containing this, as an antifouling agent due to aquatic organisms, a fishing net antifouling agent for preventing aquatic fouling organisms from attaching to and propagating on fishing nets for aquaculture or stationary use, or Effectively used as materials for floats and ropes used in ship bottoms and fishing nets, as antifouling paints, etc. to prevent underwater fouling organisms from adhering to and propagating on condenser cooling waterways in nuclear and thermal power plants. Can be used.

It has also been found that the triphenylboron-containing polymer of the present invention has a function not only as an active ingredient but also as a binder (binder), and that it is an effective ingredient with little effect on the environment.

This application is based on patent application No. 166994/1997 and patent application No. 259897/1997 filed in Japan, the contents of which are incorporated in full herein. Shall be done.

Claims

The scope of the claims

1. A homopolymer or copolymer having a repeating unit represented by the following formula (1), and a polymer having a weight average molecular weight of 100 to 100,000.

(Wherein R ′, R ² and R ³ are each selected from the group consisting of hydrogen and alkyl groups having 1-4 carbon atoms).

2. A homopolymer or copolymer having a repeating unit represented by the following formula (2), and having a weight average molecular weight of 100 to 100 000.

3. A composition comprising the triphenylboron-containing polymer according to claim 1 or 2.

4. An agent for preventing fouling by organisms attached to water, comprising the polymer containing triphenylboron according to claim 1 or 2.

5. A fishing net antifouling agent comprising the triphenylboron-containing polymer according to claim 1 or 2.

6. An antifouling paint containing the trifluorovinylboron-containing polymer according to claim 1 or 2. .

7. In addition, bis (2-pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-1oxide) copper, 2-tertiary butylamino-4, cyclopropylamino-6, methylthio-1,3,5 —Triazine, cuprous oxide, copper thiocyanate (CuSCN), alkyl acrylate, methyl methacrylate, tributyl tin methacrylate copolymer, tetraethyl thiuram disulfite, zinc dimethyl dithiocarbamate, bis (Dimethyldithiocarbamoyl) zinc dimethyl bisdithiocarbamate, pyridine-triphenylborane, trifluorobenzene Monoalkyl (3 to 30 carbon atoms) amine, triphenylborane-rosinamine, copper rhodanide, copper hydroxide, copper naphthenate, manganese ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate, N, N-Dimethyldichlorophenylurea, 4,5-dichloro-1-2-n-octyl-13-isothiazolone, N- (fluorodichloromethylthio) phthalimid, N, N, 1-dimethyl-N, -phenyl 1- (N-fluorodichloromethylthio) sulfamide, 3-method 2-provinylbutylcarbamate, jodomethylparatolylsulfone and 2- (4-thiazolyl) 1-benzoimidazole, 1,3-disia Benzene, 2 — (thiocyanomethylthio) benzothiazol, general formula (3)

(Wherein, R ⁵ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group, or a halogen-substituted benzyl group; ¹ and X ² each represent a chlorine atom), and 2,3-dichloromaleimides; And general formula (5)

(In the formula, R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents hydrogen, alkyl group, halogen-substituted alkyl group, cycloalkyl group, phenyl group, halogen, alkoxy group, carbonyl group, alkenyl group or 5. The antifouling agent for aquatic organisms according to claim 4, which contains, as an active ingredient, at least one selected from the group consisting of funinols represented by aralkyl groups.

8. In addition, 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, general formula (3)

(Wherein, R ⁴ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms), a tetraalkylthiuram disulfite represented by the general formula (4)

(Wherein, R ⁵ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group, or a halogen-substituted benzyl group; ¹ and X ² each represent a chlorine atom), 2,3-dichloromaleimides represented by the general formula (5)

(In the formula, R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents hydrogen, alkyl group, halogen-substituted alkyl group, cycloalkyl group, phenyl group, halogen, alkoxy group, carbonyl group, alkenyl group or The fishing net antifouling agent according to claim 5, which contains, as an active ingredient, at least one selected from the group consisting of phenols represented by aralkyl groups.

9. In addition, bis (2-pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-oxide) copper, 2-tertiary butylamino-4, cyclopropylamino-6, methylthio-1,3,5 — Triazine, cuprous oxide, copper thiocyanate (CuSCN), alkyl acrylate, methyl methacrylate, triptyls methacrylate copolymer, tetraethylthiuram disulfite, dimethyl dithiocarbamate zinc salt, Bis (dimethyldithiocarbamoyl) zinc dimethyl bisdithiocarbamate, pyridine-triphenylborane, triphenylborane-alkyl (3 to 30 carbon atoms) amine, triphenylborane bite ginamine, copper rhodanate, copper hydroxide, naphthene Copper oxide, manganese ethylenebisdithiocarbamate, Click ethylenebis di Chio carbamate, N, N- dimethyl dichloro off Eniru urea, 4, 5 - dichloro one 2 - n-Okuchiru 3 - isothiazolone, N- (Fluorodichloromethylthio) phthalimid, N, N'-Dimethyl-N'-phenyl (N-fluorodichloromethylthio) sulfamide, 3-Eodo-1-2-Provinylbutylcarbamate, Jodomethylparatolylsulfone and 7. The antifouling paint according to claim 6, comprising at least one selected from the group consisting of 2- (4 thiazolyl) benzoimidazole as an active ingredient.