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WO2006006415A1 - Composition à base de résine hydrophile pour un produit de revêtement et produit de revêtement contenant la composition à base de résine dispersée dans ledit produit - Google Patents

Composition à base de résine hydrophile pour un produit de revêtement et produit de revêtement contenant la composition à base de résine dispersée dans ledit produit Download PDF

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Publication number
WO2006006415A1
WO2006006415A1 PCT/JP2005/012067 JP2005012067W WO2006006415A1 WO 2006006415 A1 WO2006006415 A1 WO 2006006415A1 JP 2005012067 W JP2005012067 W JP 2005012067W WO 2006006415 A1 WO2006006415 A1 WO 2006006415A1
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WIPO (PCT)
Prior art keywords
fiber
antifouling agent
antifouling
weight
resin composition
Prior art date
Application number
PCT/JP2005/012067
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English (en)
Japanese (ja)
Inventor
Takao Shimizu
Masakazu Nishiyama
Original Assignee
Kuraray Co., Ltd
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Publication date
Application filed by Kuraray Co., Ltd filed Critical Kuraray Co., Ltd
Publication of WO2006006415A1 publication Critical patent/WO2006006415A1/fr

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    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • Patent application title Hydrophilic resin composition for coating material and coating material in which the resin composition is dispersed
  • the present invention relates to a paint having an effect of preventing aquatic organisms from sticking to a ship bottom and an underwater structure used in contact with seawater or fresh water for a long period of time.
  • the present invention relates to a fiber useful for a paint having an effect of preventing adhesion of aquatic organisms over a long period of time.
  • While these structures are in contact with seawater for a long period of time, they adhere to the surface of marine organisms, for example, algae such as guasa diatoms, coelenterates such as sea anemone, sponges such as isocaimen, annelids such as kuzumagokai, Tentacles such as bryozoans, molluscs such as mussels, arthropods such as barnacles, protozoa such as sea squirts, etc. are attached and inhabited, and the original functions of these structures cannot be fully achieved. A problem arises.
  • algae such as guasa diatoms
  • coelenterates such as sea anemone
  • sponges such as isocaimen
  • annelids such as kuzumagokai
  • Tentacles such as bryozoans
  • molluscs such as mussels
  • arthropods such as barnacles
  • protozoa such as sea squirt
  • a method of treating a product with a non-tin organic compound such as a urea compound, a benzimidazole compound, a benzothiazole compound, a thiophthalimide compound, or a sulfopyridine compound.
  • a non-tin organic compound such as a urea compound, a benzimidazole compound, a benzothiazole compound, a thiophthalimide compound, or a sulfopyridine compound.
  • a medicinal component such as a fragrance, an antifouling agent, an insect repellent, a fungicide, a poultice, or the like is sustainedly released to maintain a certain effect over a long period of time.
  • Countermeasures such as adjustment of the molecular weight of the component and introduction of functional groups, or loading a medicinal component into a microcapsule, have been made.
  • Patent Document 2 has a description example regarding 4,5-dichloro-2-n-octylisothiazolin-3-one, which is one of the antifouling agents used in the present invention.
  • the antifouling agent is extremely low toxic to the human body, which has a high antifouling effect on a variety of organisms attached to water tanks, and immediately after the antifouling action is completed, it is immediately decomposed into a completely nontoxic substance. It is clear to do.
  • an antifouling agent contained in a solvent-based paint is applied to an underwater structure and dried to form an antifouling coating film, it is effective when initially put into the sea.
  • the antifouling component is eluted or removed from the coating film in a relatively short period of time, and the effect of preventing aquatic organism adhesion is lost.
  • the antifouling agent is easily soluble in organic solvents, so that the antifouling agent also moves to the surface of the coating film as the solvent moves to the surface when the coating film dries. This is because it is not uniform.
  • paints using non-tin organic compounds which have a high aquatic organism adhesion prevention effect and have sufficient sustainability, can be obtained in both fisheries and civil engineering fields. ,is the current situation.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-139919
  • Patent Document 2 JP-A-7-69815
  • Patent Document 3 Japanese Patent Laid-Open No. 8-295829
  • Patent Document 4 Japanese Patent Laid-Open No. 11-12103
  • An object of the present invention is to provide a paint capable of preventing the adhesion of aquatic organisms over a long period of time when the antifouling agent is uniformly present in the coating film when applied to a structure used in contact with seawater or fresh water. More preferably, by providing a drug carrier suitable for a solvent-based paint having excellent chemical solution retention after xylene washing, that is, excellent sustained release of medicinal ingredients and long-term antifouling properties. is there.
  • the present invention relates to a hydrophilic resin composition containing a compound having an antifouling property, and preferably the compound having an antifouling property is a compound represented by the following general formula (1):
  • the above-mentioned hydrophilic resin composition which is a complex compound of a metal salt or an amine salt.
  • Y represents a hydrogen atom, an alkyl group, a alkenyl group, or an aralkyl group
  • R represents a hydrogen atom, a halogen atom, or an alkyl group
  • R ′ represents a hydrogen atom, a halogen atom, or an alkyl group.
  • R and R ' may combine to form a benzene ring.
  • the present invention is preferably the above-described hydrophilic rosin composition in which the hydrophilic resin is polybulal alcohol-based rosin, and more preferably, the hydrophilic resin has a fiber component of 60 wt% Z. It is a hydrophilic resin composition for paints, characterized by having a polybulal alcohol strength higher than that of fibers and satisfying all of the following 1) to 3).
  • the fiber has a skin core structure and the core ratio is 50% or more
  • the fineness of the fiber is 0.1 to 30dtex, the fiber length is 3mm or less,
  • the antifouling agent component according to claim 2 is supported by 10% by weight Z fiber or more, and the antifouling agent retention rate after washing with xylene represented by the following formula is 80% or more,
  • Antifouling agent retention after xylene cleaning (Antifouling agent retention after cleaning Z Antifouling agent retention before cleaning) X 100 (%)
  • the present invention relates to a method for producing a hydrophilic resin composition for paints, characterized by impregnating the fiber cut to 3 mm or less in a solution in which a drug component is dissolved in methanol. More preferably, a coating film-forming binder is contained, and the coating film-forming binder is the above-described coating liquid and coating film having self-polishing properties, and is formed by coating the above-described coating liquid with water. It relates to structures.
  • the hydrophilic rosin composition of the present invention is obtained by solidifying and gelling a water-soluble polymer compound as a rosin component, and is obtained by polybulal alcohol (hereinafter abbreviated as PVA), sodium polytalylate.
  • PVA polybulal alcohol
  • Synthetic water-soluble polymer compounds such as polyethylene glycol and polyethyleneimine, and natural waters such as alkali metal alginate, carrageenan, mannan and chitosan Soluble polymer polysaccharides can be used, but they have many hydroxyl groups that are not only excellent in mechanical performance and chemical resistance, but other molecules due to intermolecular and intramolecular hydrogen bonding.
  • PVA resin having a large barrier effect against water is preferably used.
  • the PVA resin Since the PVA resin has a polymer structure as described above, it is excellent in sustained release of a substance incorporated in the polymer. Therefore, by dispersing the PVA resin composition containing the antifouling agent, a coating film having excellent antifouling effect can be obtained.
  • the PVA-based resin preferably used in the present invention is a resin containing a vinyl alcohol-based polymer. It does not matter if it contains other polymers or other components. However, in terms of the physical performance of the resin and the sustainability of the antifouling effect, the content of the butyl alcohol polymer is 60% by mass or more ZPVA, especially 80 to: LOO% by mass ZPVA.
  • a preferred butyalcohol-based polymer constituting the hydrophilic resin of the present invention is not particularly limited as long as it has a butyal alcohol unit as a main component, and may have other constituent units.
  • comonomers examples include olefins such as ethylene, propylene, and butylene, acrylic acid and its salts and acrylic esters such as methyl acrylate, methacrylic acid and its salts, methacrylic esters such as methyl methacrylate, and acrylamide.
  • N Acrylamide derivatives such as methyl acrylamide, Methacrylamide, Methacrylamide derivatives such as N-methylol methacrylamide, N-Burpyrrolidone, N-Burformamide, N-Buramide such as N-Buracetoamide, Polyalkyleneoxide side chain Butyl ethers such as methyl butyl ether, -tolyls such as atari mouth nitrile, halogenated burs such as butyl chloride, maleic acid and salts thereof, anhydrides or esters thereof, and the like.
  • the method for introducing the modified unit may be a copolymerization method or a post-reaction introduction method.
  • the barrier properties of rosin can be further enhanced.
  • ethylene is copolymerized, the crystal form of the ethylene unit and the bull alcohol unit are similar, and the crystallinity of the PVA is unlikely to decrease, so the content of the bull alcohol unit is reduced. However, excellent performance is maintained.
  • point force sustained mechanical performance and antifouling effect of ⁇ composition also includes bi - Ri force of alcohol units used Bulle alcohol polymer of 80-100 mole 0/0 preferred.
  • the degree of hatching or degree of polymerization of the vinyl alcohol-based polymer constituting the hydrophilic resin composition there are no particular limitations on the degree of hatching or degree of polymerization of the vinyl alcohol-based polymer constituting the hydrophilic resin composition, but from the viewpoint of ensuring the durability of water resistance, mechanical performance, antifouling performance, etc.
  • the acidity is 90 mol% or more, particularly 95 mol% or more, more preferably 98 mol% or more, and more preferably 99 to 100 mol%
  • the degree of polymerization is 500 or more, particularly 1000 or less. Furthermore, 1300 or more is preferable. If the degree of polymerization is 20000 or more, it is difficult to produce industrially with the current technology, so a degree of polymerization of 20000 or less is practically used.
  • the hydrophilic rosin composition of the present invention contains a compound having a basic structure represented by the following general formula (1) (hereinafter sometimes simply referred to as "antifouling agent"). Being good!
  • Y represents a hydrogen atom, an alkyl group, an alkenyl group, or an aralkyl group.
  • the alkyl group is preferably a methyl group, butyl group, hexyl group, octyl group, nor group, dodecyl group or the like.
  • a alkenyl group having 2 to 18 carbon atoms such as a bur group and an isopropyl group is preferred.
  • the aralkyl group is preferably an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, a phenethyl group, or a 4-methoxybenzyl group.
  • R represents a hydrogen atom, a halogen atom or an alkyl group
  • R ′ represents a hydrogen atom, a halogen atom or an alkyl group.
  • the halogen atom in R and R ′ is preferably chlorine, bromine, fluorine or the like.
  • the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group.
  • R and R ' may combine to form a benzene ring.
  • Such compounds include 2-methyl-4 isothiazoline-3-one, 2-methyl-5chloro 4-isothiazoline-3-one, 1,2 benzoisothiazolin-3one, 2 --N—Octylisothiazoline-3one, 4,5 Dichloro 2-n—octylisothiazoline-3-one, etc.
  • R and R ' are halogen atoms. It is desirable that Y is an alkyl group having 1 to 9 carbon atoms, and 4,5-di-2-n-oct-4-isothiazolin-3-one is the most preferred compound.
  • These compounds include zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, copper chloride, copper bromide, nickel chloride, calcium chloride, magnesium chloride, iron chloride, manga chloride. May be combined with metal salts such as sodium chloride, sodium chloride and barium chloride, and amine salts such as salt ammonium and other amine chlorides to form complex compounds. .
  • Polybulal alcohol (hereinafter abbreviated as PVA) that is suitably used as the hydrophilic resin composition of the present invention is not only excellent in various performances such as mechanical performance and chemical resistance, but also in hydroxy acid. It is suitable for the purpose of the present invention, which has a large number of groups and has a large noria effect on solvent molecules due to intermolecular and intramolecular hydrogen bonding.
  • the component constituting the fiber that is preferably used as a fiber cannot obtain desired performance if it is mainly composed of strong PVA.
  • it is preferably composed of PVA fibers of 60 wt% Z fibers or more, preferably 80 wt% Z fibers or more and 100 wt% Z fibers or less.
  • PVA fibers preferably used in the present invention preferably have a skin core structure and a core ratio of 50% or more.
  • the antifouling agent supported on the fiber is a low crystalline In order to carry more antifouling agent, it is preferable that the ratio of the core portion is high.
  • the core ratio is the ratio of the cross-sectional area of the core layer to the cross-sectional area of the fiber and is defined by the following equation.
  • Core ratio (core layer cross-sectional area Z cross-sectional area of the entire fiber) X loo (%)
  • the cross-sectional area of the entire fiber includes both the skin layer and the core layer. Further, in the measurement, the cross section of the fiber is observed with an optical microscope, and the portion where the light is well transmitted and visible is defined as the skin layer, and the portion which is transmitted and appears dark is defined as the core layer. Depending on the manufacturing method, the difference in skin core structure may not be discernable, but in some cases it cannot be discriminated! / In this case, it is assumed that the core layer does not exist (core ratio 0%).
  • the fineness of the fibers is 0.1 to 30 dtex and the fiber length is 3 mm or less. Those having a fineness of less than 0. ldtex are difficult to disperse in the paint and it is difficult to produce fibers.
  • the fineness is 30dtex or more, the uniformity of the paint and coating film is poor. More preferably, it is 1 to 15 dtex.
  • the fiber length is 3 mm or more, it is difficult to mix into the paint, preferably 2 mm or less, more preferably 1 mm or less and 0.1 mm or more.
  • a shorter fiber length is advantageous in that the treatment can be performed in a shorter time.
  • the loading rate is preferably 10% by weight or more, more preferably 20% by weight or more, more preferably 25% by weight or more and 40% by weight or less.
  • the main purpose of the present invention is to prevent the extraction by the solvent, and the degree of the anti-extraction is expressed by the antifouling agent retention after the xylene cleaning. Specifically, an operation of positively extracting the fiber carrying the antifouling agent by immersing it in xylene at 65 ° C with a bath ratio of 100 for 5 hours is expressed by the following formula.
  • Anti-fouling agent loading after washing Z Anti-fouling agent carrying rate before washing
  • anti-fouling agent retention after xylene washing is 80% or more Preferably, it is 90% or more and 100% or less.
  • the fiber which is a preferred form of the present invention may contain a force PVA-based copolymer of PVA and other monomers or other components.
  • the PVA content is 60% by weight, 7 fibers or more, especially from the viewpoint of the physical performance of the fat and the durability of the antifouling effect.
  • 80 ⁇ : L00% by weight Z fibers are preferred.
  • the copolymerizable monomer include olefins such as ethylene, propylene, and butylene, acrylic acid and salts thereof and acrylic esters such as methyl acrylate, methacrylic acid and salts thereof, and methacrylic esters such as methyl methacrylate.
  • Acrylamide derivatives such as acrylamide and N-methylacrylamide, methacrylamide such as methacrylamide and N-methylolmethacrylamide
  • N-Burpyrrolidone N-Burformamide
  • N-Buramides such as N-Buracetoamide
  • Aryl ethers having polyalkyleneoxide in the side chain Bul ethers such as methyl bull ether, Acrylonitrile, etc.
  • Tolyls halogenated butyls such as butyl chloride, maleic acid and its salts or anhydrides and their esters;
  • inorganic materials such as calcium carbonate, aluminum hydroxide and titanium oxide are used as the raw material for spinning. When mixed and spun into the liquid, fine voids are formed on the surface of the fiber, which facilitates the penetration of the phenol and, as a result, increases efficiency. This effect can also be expected for porous inorganic materials such as silica, activated carbon and zeolite.
  • the barrier property of rosin can be further enhanced.
  • ethylene is copolymerized, the crystal morphology of the ethylene unit and the bull alcohol unit are similar, and the crystallinity of PVA is unlikely to deteriorate, so that even if the content of the bull alcohol unit is small, excellent performance is achieved. Retained.
  • the point forces sustained mechanical performance and antifouling effect of ⁇ composition also includes bi - Ri force of alcohol units used Bulle alcohol polymer of 80-100 mole 0/0 preferred.
  • the degree of polymerization and degree of polymerization of PVA the degree of chaininess is 95 mol% or more from the viewpoint of ensuring water resistance, mechanical performance, durability of antifouling performance, etc. Furthermore, it is preferable that the degree of polymerization is 500 or more, particularly 1000 or more, more preferably 1300 or more and 5000 or less for the same reason that it is preferably 98 mol% or more, and further 99-: LOO mol%.
  • the fiber which is a preferred form in the present invention is advantageous in that it has a non-uniform structure in the cross-sectional direction, that is, a so-called skin core structure.
  • a remarkable effect can be expected for fibers having a core ratio of 50% or more. It is estimated that the low crystallinity core portion swells easily with methanol, and the antifouling agent dissolved in methanol is infiltrated and adsorbed.
  • the fiber shape when immersed in a methanol bath of the drug is preferably cut short. This is because the antifouling agent easily penetrates from the cut end face.
  • the fiber length is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less and 0.1 mm or more. If it is 3mm or more, it will be difficult to mix in the paint.
  • the method for producing a fiber having a strong skin core structure is not particularly limited, but a general method, that is, a solution in which PVA is dissolved in water is used as a spinning dope and has a coagulating ability such as a nozzle cap. Extruded into a bath by wet or dry wet method, solidified, wet-stretched and dried according to a conventional method • Obtained by the method of dry heat stretching 'heat treatment.
  • the concentration of the spinning dope may be adjusted as appropriate according to the polymerization of the PVA, but if it is a general one having a polymerization degree of 1500 to 2000, it is easy to adjust with 13 to 18% by weight Z fiber. The lower the concentration, the higher the core ratio at which a skin core structure can be easily formed.
  • a sodium sulfate bath is generally used, but ammonium sulfate, kenate or the like may be used. The closer these salts are to saturation, the better the coagulability.
  • the strength of the acetalization treatment is applied after the dry heat stretching 'heat treatment to supplement the water resistance.
  • a higher degree of swelling is preferred. If it is desirable to dissolve in water for the purpose of use, do not perform the acetalization process, but provide only the minimum required water resistance.
  • the above-mentioned minimum required water resistance means that the salt having a dehydrating ability attached to the fiber can withstand washing and drying. It is desirable that such salts be removed by washing in any of the steps before being immersed in the methanol solution of the drug.
  • washing tank before drying there are a method of passing through a washing tank before drying, or a method of washing and drying after dry heat stretching and heat treatment, but the latter is preferable because there is less concern about sticking and high production efficiency. .
  • a fiber having a fiber length of 3 mm or less as described above is immersed in a solution in which the antifouling agent is dissolved in methanol, and the fiber is swollen with methanol to allow the antifouling agent to penetrate into the fiber.
  • the reason for using methanol is that methanol is a good solvent widely for various chemicals, and has a moderate affinity for PVA fibers, which involves destruction of fiber structures such as sticking and dissolution. This is because it is possible to swell the PVA fiber without any problems.
  • the concentration and temperature of the solution may be appropriately adjusted according to the solubility of the antifouling agent and the target loading amount, but the treatment can be performed in a short time in the direction of high temperature and high concentration.
  • a component that swells the PVA fiber In order to more efficiently infiltrate the antifouling agent, it is also effective to use a component that swells the PVA fiber.
  • liquid and methanol such as glycerin, ethylene glycol, sorbitol, and pentaerythritol Compatible polyhydric alcohols, boric acid and form Aldehydes and the like can also be used as swelling agents.
  • the blending ratio of these components should be set as appropriate so long as it does not inhibit the solubility of the antifouling agent, and does not cause excessive swelling of the PVA fiber or dissolution! / ⁇ .
  • an antifouling agent that easily enters sebum tends to ooze out from sebum (in the present invention, PVA fiber), that is, tends to bleed out.
  • PVA fiber in the present invention, PVA fiber
  • Strength in the present invention, in particular, when a PVA fiber having a skin core structure is used, since the antifouling agent is adsorbed in the voids of the core layer, the bleed-out hardly occurs. It is also possible to enhance the bleed-out suppression effect by impregnating the antifouling agent and then drying or further applying heat treatment to crystallize the polymer.
  • the antifouling agent adhering to the surface has no effect of sustained release, so it is economical to recover it by washing with a solvent.
  • the solvent used here can be used as long as it dissolves the drug without causing the PVA fiber to swell so much, but it is the same type of solvent used for impregnation as the impregnation power, such as the recovery of antifouling agents. Methanol is preferred. At that time, it is desirable to carry out at a lower temperature than the impregnation treatment in order to prevent the extraction of the antifouling agent when the fiber swells.
  • the fiber of the present invention obtained in this way is suitable as an additive to a paint that expects a sustained release effect of an antifouling agent, and in particular, a ship bottom used in contact with seawater or fresh water for a long time, By applying to an underwater structure and forming a coating film, the intended effect of the present invention is exhibited.
  • the coating film-forming binder contained in the coating liquid of the present invention is preferably self-polishing.
  • the antifouling agent does not migrate to the coating surface over time, so that the antifouling agent can be stably immersed in water.
  • rosin compositions have been proposed in order to elute cuprous oxide.
  • water-soluble rosin such as rosin-based rosin, methyl vinyl ether, N-bulurpyrrolidone, methoxyethylene glycol methacrylate, acrylamide, methyl triacetoxysilane 'methyl acrylate, 2-hydroxy acrylate copolymer, butyl triacet
  • xysilane 'methyl meta atallylate' butyl acetate copolymer Slightly hydrolyzable rosin, and copolymers and mixtures thereof are used.
  • These binders are appropriately used as necessary, but are not particularly limited.
  • the organic solvent used in the coating liquid of the present invention includes aliphatic hydrocarbons such as hexane, heptane, rigging-in, and petroleum ether, and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Halogenated hydrocarbons such as chloroform, formaldehyde, carbon tetrachloride, dichloroethane, benzene, dichlorobenzene, ketones such as acetone, methylethylketone, methylisobutylketone, isophorone, cyclohexanone, formic acid , Fatty acids such as acetic acid and oleic acid, methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol, methylcelesolve, diethylene glycol, glycerin and other alcohols, ethyl formate, ethyl acetate, butyl acetate, jetyl carbonate, etc.
  • Halogenated hydrocarbons such as chloroform, formaldehyde, carbon tetrachloride, dichloroethane, benzene, dichlorobenzene, ketones such as
  • esters such as nitroethane, nitrobenzene, etc.
  • -Tolyls such as acetonitrile, isobutyric-tolyl, pyridine, triethylamine, tertiary amines such as N, N-jetylaniline, tributylamine, N-methylmorpholine, formamide, N, N-dimethylformamide, Acid amides such as acetoamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, or mixtures thereof are used.
  • the thickness of the coating film formed from the paint of the present invention is not particularly limited, but in order to maintain the antifouling effect for a long time, it is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more.
  • the underwater structure means, for example, a structure, a fibrous material, a resin processed cloth, a rope, a woven fabric, a knitted fabric, a net, a non-woven structure in which at least a part of the above-mentioned coating film is coated or impregnated.
  • a woven fabric, a film, etc. the form is not limited to these, and it is intended for all structures having various forms in which the effects of the present invention can be achieved depending on the use.
  • the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
  • the content of the antifouling agent in the hydrophilic rosin composition was measured by the following method.
  • hydrophilic rosin composition sample Take 0.1 lg of hydrophilic rosin composition sample, add 20 ml of dimethyl sulfoxide to dissolve, sample 30 ml of acetonitrile, standardize to 50 ml, and filter through a 0.45 ⁇ filter. A sample solution was obtained. This was analyzed by high-performance liquid chromatography based on a calibration curve prepared with a standard solution for analysis prepared using 4,5-dichloro-1-n-octyl-4-isothiazolin-3-one standard substance. .
  • HPLC6A system unit manufactured by Shimadzu Corporation
  • UV wavelength 275nm
  • PVA with a degree of polymerization of 1700 and a degree of hatching of 99.9 mol% was dissolved in water at a concentration of 13 wt% Z fiber, and wet-spun into a 40 ° C saturated sodium sulfate bath through a 1000-hole spinning nozzle. It was taken out at a speed of / min, then stretched by 3.0 times, and further wet stretched by 1.5 times in a saturated sodium sulfate bath at 90 ° C and dried. The resulting fiber has a core ratio of 60% and a fineness of 2. Odtex.
  • the antifouling agent loading of the fiber obtained in 2) above is 15% by weight Z fiber, and the antifouling agent loading measured after immersion for 5 hours in xylene at 65 ° C with a bath ratio of 100 13.8 wt% Z fiber, that is, the antifouling agent loading after xylene cleaning was 92%.
  • this shinoshino was used as an antifouling agent in a methanol solution containing 50% by weight of Z fiber.
  • the dried yarn was cut into 3 mm to obtain a fiber having antifouling performance.
  • the antifouling agent loading after 3 mm cutting of the obtained fiber was 8 wt% Z fiber, and this was measured for the antifouling agent loading after dipping in 65 ° C xylene for 5 hours at a bath ratio of 100.
  • the antifouling agent loading after xylene cleaning was 85%.
  • Example 1 Exactly the same treatment as in Example 1 was performed, except that 35% by weight of polyacrylic acid having a molecular weight of 5000 and 65% by weight of PVA were added to the spinning dope.
  • the resulting fiber has an antifouling agent loading rate of 20% by weight 7 fibers, and the antifouling agent loading rate measured after immersion in xylene at 65 ° C for 65 hours at a bath ratio of 100 is 17% by weight Z fiber. That is, the antifouling agent loading after xylene cleaning was 85%.
  • the obtained shinoshino was subjected to DMSO extraction in a methanol bath substantially completely, and 3.0 times wet stretching was performed to swell the organic solvent (methanol) content to 140 wt% Z fiber. I got Ishinoshino.
  • this gel particle 4 as an antifouling agent, 5-dichloro-one 2-n-Okuchinore one 4- Isochi Azorin one 3-one (methanol solution KATHON287T Rohm & made Haas) and containing 30 weight 0/0
  • methanol solution KATHON287T Rohm & made Haas methanol solution KATHON287T Rohm & made Haas
  • the resin particles were pulverized to obtain a hydrophilic resin composition having an antifouling performance with an average particle diameter of 20 m.
  • 60 parts by weight of the antifouling hydrophilic resin composition of Example 2 is 40 parts by weight of bisphenol A type liquid resin having an epoxy equivalent of 184 to 194, 20 parts by weight of a curing agent, and 25 parts by weight of calcium carbonate.
  • an antifouling agent 20 parts by weight of 4,5 dichloro-2 n-octyl 4 isothiazoline 3 -on was dispersed in the paint and applied to an acrylic plate having a thickness of 3 mm ⁇ 50 cm ⁇ 50 cm. The coating thickness after drying was 200 m.
  • Example 2 Except for adding 45% by weight of polyacrylic acid having a molecular weight of 5000 and 55% by weight of PVA to the spinning dope, the same treatment as in Example 1 was performed.
  • the obtained fiber had an antifouling agent loading rate of 24% by weight and 7 fibers, and the antifouling agent loading rate measured after immersion in xylene at 65 ° C for 65 hours at a bath ratio of 100 was 17.5% by weight. It was Z fiber, that is, the antifouling agent loading after washing with xylene was 73%.
  • a paint and a coating film were prepared in the same manner as in Example 1, and immersed in the sea in Omeyama Bay in Okayama Prefecture, and the state of aquatic organism adhesion was regularly observed, but no organisms adhered. It was only for 6 months.
  • Example 1 when the fiber length was 5 mm, the antifouling agent loading was 6%. When the fiber length was long, penetration of the antifouling agent occurred and was difficult. When the fiber length was 5 mm, it was difficult to add to the paint because the fiber length was too long.
  • Example 6 The solvent of the antifouling agent in Example 1 was replaced with methanol, and methyl isobutyl ketone (Comparative Example 6) and xylene (Comparative Example 7) were used.
  • the anti-fouling agent loading ratio of the obtained fibers was 2% or less, both of which were very low. Both solvents hardly swell fibers that have no affinity with PVA. Methanol is suitable as a solvent that swells PVA moderately.
  • the structure coated with the antifouling coating liquid of the present invention prevents adhesion of aquatic organisms over a long period of time even when immersed in water, has excellent durability, and is environmentally friendly.
  • Ships, power plant cooling water intake facilities, subsea oil field drilling facilities, coastal industrial plants, port facilities, large structures such as bridges, and fishery materials such as fishery nets Can be used for ship materials such as navigation buoys, light buoys and mooring buoys, and civil engineering materials such as pollution control curtains.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
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  • Paints Or Removers (AREA)

Abstract

Composition à base de résine hydrophile qui contient un agent antisalissure d’isothiazoline et qui peut empêcher, sur une longue période, l’adhésion des organismes aquatiques. La composition à base de résine hydrophile contient de préférence un ingrédient fibreux comprenant des fibres d’alcool polyvinylique parmi lesquelles au moins 60 % en poids ont une structure peau-cœur et qui ont une partie centrale de 50 % ou supérieure, une finesse de fibres de 0,1 à 30 dtex et une longueur de fibres de 3 mm ou plus courte. Ladite composition comporte l’agent antisalissure déposé sur elle-même en une quantité de 10 % en poids ou supérieure sur la base du poids des fibres et a une rétention de l’agent antisalissure après lavage avec du xylène de 80 % ou supérieure. L’invention concerne également un fluide de revêtement auto-abrasif pour les structures sous-marines qui contient la composition à base de résine hydrophile dispersée en lui-même, et une couche protectrice.
PCT/JP2005/012067 2004-07-08 2005-06-30 Composition à base de résine hydrophile pour un produit de revêtement et produit de revêtement contenant la composition à base de résine dispersée dans ledit produit WO2006006415A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2004201261 2004-07-08
JP2004-201261 2004-07-08
JP2005173809 2005-06-14
JP2005-173809 2005-06-14

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WO2006006415A1 true WO2006006415A1 (fr) 2006-01-19

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TW (1) TW200606227A (fr)
WO (1) WO2006006415A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016502574A (ja) * 2012-11-06 2016-01-28 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 防汚塗料系
NL2034927A (en) * 2022-05-31 2023-12-07 Chugoku Marine Paints Antifouling coating composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6566554B2 (ja) * 2014-08-20 2019-08-28 昭和電工株式会社 積層シートおよび積層シートの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04146212A (ja) * 1990-10-08 1992-05-20 Kuraray Co Ltd 海棲生物付着防止効果を有する親水性繊維およびその製造方法
JPH09157111A (ja) * 1995-12-06 1997-06-17 Toyobo Co Ltd 生物抵抗性成型品、その製造方法およびそれを用いた製品
JPH09273073A (ja) * 1996-04-01 1997-10-21 Toyobo Co Ltd 生物抵抗性を有する繊維製品の加工方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04146212A (ja) * 1990-10-08 1992-05-20 Kuraray Co Ltd 海棲生物付着防止効果を有する親水性繊維およびその製造方法
JPH09157111A (ja) * 1995-12-06 1997-06-17 Toyobo Co Ltd 生物抵抗性成型品、その製造方法およびそれを用いた製品
JPH09273073A (ja) * 1996-04-01 1997-10-21 Toyobo Co Ltd 生物抵抗性を有する繊維製品の加工方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016502574A (ja) * 2012-11-06 2016-01-28 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 防汚塗料系
NL2034927A (en) * 2022-05-31 2023-12-07 Chugoku Marine Paints Antifouling coating composition

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