WO1998033829A1 - Polymere a teneur en triphenylbore et utilisation correspondante - Google Patents

Polymere a teneur en triphenylbore et utilisation correspondante Download PDF

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Publication number
WO1998033829A1
WO1998033829A1 PCT/JP1998/000375 JP9800375W WO9833829A1 WO 1998033829 A1 WO1998033829 A1 WO 1998033829A1 JP 9800375 W JP9800375 W JP 9800375W WO 9833829 A1 WO9833829 A1 WO 9833829A1
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group
weight
alkyl
halogen
copper
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PCT/JP1998/000375
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English (en)
Japanese (ja)
Inventor
Akira Shimada
Masanori Kohara
Yoshifumi Shibuya
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Yoshitomi Fine Chemicals, Ltd.
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Publication of WO1998033829A1 publication Critical patent/WO1998033829A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups

Definitions

  • 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.
  • 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.
  • 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.
  • a fishing net fujibo 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.
  • 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.
  • 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.
  • 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.
  • the conventional antifouling agent described above has a weaker effect of preventing adhesion to helminths such as helminths and devisia, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention is as follows.
  • 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) ).
  • R ′, R 2 and R 3 are each selected from the group consisting of hydrogen and an alkyl group having 1-4 carbon atoms.
  • R 4 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms
  • 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)
  • 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:
  • R 4 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms
  • 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.
  • 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
  • FIG. 1 shows an IR (infrared) spectrum of the polymer obtained in Synthesis Example 1.
  • 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.
  • an arylamine-type polymer can be synthesized by the method shown in the following formula.
  • amine examples include arylamine, 2-methylarylamine, 3-methylarylamine, 2,3-dimethylarylamine, 2-ethylarylamine, 3-ethylarylamine, 2-butylarylamine, and the like. Is mentioned.
  • triphenyl which is the desired arylamine-type polymer, is obtained.
  • a ruborone-containing polymer can be synthesized.
  • 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 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.
  • ethylenically unsaturated monomer examples include ethylene, propylene, butadiene, isoprene, styrene, indene, acrylonitrile, vinyl ethers, acrylic esters, methacrylic esters, and the like.
  • the vinylamine type polymer can be synthesized by the method shown in the following formula.
  • 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.
  • ethylenically unsaturated monomer examples include ethylene, propylene, butadiene, isoprene, styrene, indene, acrylonitrile, vinyl ethers, acrylic esters, methacrylic esters, and the like.
  • 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.
  • a polymer containing triflate boron when used as an antifouling agent for fishing nets, 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.
  • 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.
  • an aromatic organic solvent 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.
  • an aromatic organic solvent 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.
  • 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.
  • tetraalkylthiuram disulfides (3) include tetramethyl thiuram disulfides. Ruthiuram disulfide, tetraethylthiuram disulfide, tetraisopropyl thiuram disulfide, tetra-n-butylthiuram disulfide, and the like.
  • 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
  • alkyl group for R 5 examples 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.
  • a cycloalkyl group such as a cyclohexyl group is preferable.
  • the alkyl-substituted phenyl group include a dimethylphenyl group, a getylphenyl group, a methylethylphenyl group and the like.
  • the halogen-substituted phenyl group include a dichlorophenyl group.
  • the alkyl-substituted benzyl group include a methylbenzyl group, a dimethylbenzyl group, a acetylbenzyl group, and a monomethylbenzyl group.
  • the halogen-substituted benzyl group include a chlorobenzyl group and a dichlorobenzyl group.
  • 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—
  • 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.
  • alkoxy group examples include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group.
  • alkenyl group examples include those having 2 to 4 carbon atoms such as a vinyl group, an aryl group and an isopropyl group.
  • aralkyl group the number of carbon atoms such as benzyl group and cumyl group? ⁇ 9.
  • 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.
  • a dissolution modifier used in fishing net antifouling agents a general formula (6)
  • R 9 represents an alkyl group having 1 to 20 carbon atoms, and m represents an integer of 2 to 10).
  • alkyl group for R 9 examples 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.
  • 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.
  • 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.
  • silicone oils examples include dimethyl silicone oil, higher fatty acid-modified silicone oil, alkyl-modified silicone oil, and methylphenylsilicone oil.
  • the polymer containing trifluoropropylone of the present invention 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.
  • 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.
  • 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,
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • the formulation of the comparative example is as follows.
  • Evaluation B Fishing net fouled area 0 to 10%. Slight adherent organisms are present, but practically acceptable.
  • Evaluation D Fishing net fouled area 50% or more. Extremely large amount of organisms attached.
  • 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.
  • 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.
  • Tetopen 1000 Z26, 3rd dimension
  • 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. .
  • 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.
  • 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.
  • 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.
  • the components were mixed and dispersed at the following coating composition ratio to obtain an antifouling paint.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention se rapporte à un homopolymère ou un copolymère comprenant des unités répétitives représentées par la formule (1) ou (2) et ayant un poids moléculaire moyen en poids compris entre 1,000 et 1,000,000, ainsi qu'à un agent antisalissure servant à combattre les salissures marines et contenant un tel composé. Ledit agent antisalissure diminue considérablement l'adhérence des salissures marines et possède une excellente action antisalissure. Ledit polymère à teneur en triphénylbore fonctionne non seulement comme principe actif mais également comme liant. Il porte moins atteinte à l'environnement.
PCT/JP1998/000375 1997-01-30 1998-01-28 Polymere a teneur en triphenylbore et utilisation correspondante WO1998033829A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP1669497 1997-01-30
JP9/16694 1997-01-30
JP9/259897 1997-09-25
JP25989797A JP2002161115A (ja) 1997-01-30 1997-09-25 トリフェニルボロン含有ポリマー

Publications (1)

Publication Number Publication Date
WO1998033829A1 true WO1998033829A1 (fr) 1998-08-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/000375 WO1998033829A1 (fr) 1997-01-30 1998-01-28 Polymere a teneur en triphenylbore et utilisation correspondante

Country Status (2)

Country Link
JP (1) JP2002161115A (fr)
WO (1) WO1998033829A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1086996A1 (fr) * 1999-09-21 2001-03-28 Nippon Paint Co., Ltd. Résine incorporée dans un revêtement antisalissure et revêtement antisalissure
EP1245592A1 (fr) * 2001-03-28 2002-10-02 Nippon Paint Co., Ltd. Composition de résine, procédé de préparation de polymères contenant du bore et revêtement antisalissure
JP4806884B2 (ja) * 1999-07-21 2011-11-02 株式会社エーピーアイ コーポレーション トリフェニルボロン含有ポリマーおよびその用途

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4780977B2 (ja) * 2005-03-01 2011-09-28 大阪化成株式会社 腹足類の駆除剤

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08295609A (ja) * 1995-02-27 1996-11-12 Yoshitomi Pharmaceut Ind Ltd トリフェニルボラン−ｎ−オクタデシルアミン錯化合物と有機溶剤からなる溶液とその用途
JPH08311074A (ja) * 1995-03-15 1996-11-26 Yoshitomi Pharmaceut Ind Ltd トリフェニルボランアミン錯化合物の製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08295609A (ja) * 1995-02-27 1996-11-12 Yoshitomi Pharmaceut Ind Ltd トリフェニルボラン−ｎ−オクタデシルアミン錯化合物と有機溶剤からなる溶液とその用途
JPH08311074A (ja) * 1995-03-15 1996-11-26 Yoshitomi Pharmaceut Ind Ltd トリフェニルボランアミン錯化合物の製造法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4806884B2 (ja) * 1999-07-21 2011-11-02 株式会社エーピーアイ コーポレーション トリフェニルボロン含有ポリマーおよびその用途
EP1086996A1 (fr) * 1999-09-21 2001-03-28 Nippon Paint Co., Ltd. Résine incorporée dans un revêtement antisalissure et revêtement antisalissure
US6462102B1 (en) 1999-09-21 2002-10-08 Nippon Paint Co., Ltd. Resin for use in an antifouling coating and antifouling coating
EP1245592A1 (fr) * 2001-03-28 2002-10-02 Nippon Paint Co., Ltd. Composition de résine, procédé de préparation de polymères contenant du bore et revêtement antisalissure
US6753397B2 (en) 2001-03-28 2004-06-22 Nippon Paint Co., Ltd. Resin composition, production method of boron-containing polymer and antifouling coating
SG108841A1 (en) * 2001-03-28 2005-02-28 Nippon Paint Co Ltd Resin composition, production method of boron-containing polymer and antifouling coating

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