WO2006077738A1 - Composition de revêtement à l'épreuve des taches hydraulique, film de revêtement à l'épreuve des taches et structure immergée sous l'eau - Google Patents

Composition de revêtement à l'épreuve des taches hydraulique, film de revêtement à l'épreuve des taches et structure immergée sous l'eau Download PDF

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Publication number
WO2006077738A1
WO2006077738A1 PCT/JP2005/024116 JP2005024116W WO2006077738A1 WO 2006077738 A1 WO2006077738 A1 WO 2006077738A1 JP 2005024116 W JP2005024116 W JP 2005024116W WO 2006077738 A1 WO2006077738 A1 WO 2006077738A1
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WIPO (PCT)
Prior art keywords
aqueous
group
composition according
resin
water
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PCT/JP2005/024116
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English (en)
Japanese (ja)
Inventor
Kazuaki Masuda
Isamu Onishi
Naoki Yamamori
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Nippon Paint Co., Ltd.
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Publication date
Priority claimed from JP2004379674A external-priority patent/JP2006182956A/ja
Priority claimed from JP2004379673A external-priority patent/JP2006182955A/ja
Priority claimed from JP2005368799A external-priority patent/JP2007169449A/ja
Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Priority to CN2005800452760A priority Critical patent/CN101094899B/zh
Priority to GB0712694A priority patent/GB2435602B/en
Publication of WO2006077738A1 publication Critical patent/WO2006077738A1/fr

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    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • 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
    • C09D5/1687—Use of special additives

Definitions

  • the present invention relates to an aqueous curable antifouling coating composition, an antifouling coating film and an underwater structure.
  • Marine organisms such as barnacles, mussels, and algae attach to ships, fishing nets, and other underwater structures, causing problems such as hindering efficient operation and causing waste of fuel in ships. In addition, problems such as clogging in fishing nets and shortened service life occur.
  • an antifouling coating film is formed on the surface of the underwater structures.
  • an antifouling paint used for the formation of such an antifouling coating film a solvent-based paint composition containing a non-curing resin is known (for example, see Patent Documents 1 to 5).
  • Patent Documents 6 and 7 describe compositions containing a resin containing a divalent metal, water, and a basic compound. However, such a resin is non-curing type, and the water resistance of the obtained coating film was not sufficient.
  • Patent Document 1 Japanese Patent Laid-Open No. 9 52803
  • Patent Document 2 Japanese Patent Laid-Open No. 10-59810
  • Patent Document 3 Japanese Patent Application Laid-Open No. 11 172159
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2000-109729
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-371166
  • Patent Document 7 Japanese Unexamined Patent Publication No. 2003-49123
  • the present invention provides an aqueous curable antifouling paint composition that exhibits an excellent function as an antifouling paint, an antifouling coating film obtained thereby, and an underwater structure having the same. It is intended to serve.
  • the cured aqueous binder component is decomposed by water.
  • the aqueous binder component is cured by dehydration condensation.
  • the aqueous binder component preferably has at least one curing system among a carbonyl Z hydrazide system, an acetacetoxy Z amine system and an alkoxysilyl condensation system.
  • the aqueous binder component is an emulsion resin and a hardener power, and the emulsion resin preferably has a group capable of reacting with the functional group of the hardener.
  • a cured product of the aqueous binder component may have a structure in which long-chain hydrocarbon groups are cross-linked.
  • the aqueous binder component is cured by acid-sodium polymerization.
  • the oxidative polymerization preferably involves a group derived from a higher unsaturated fatty acid.
  • the aqueous binder component is preferably an emulsion resin having a higher unsaturated fatty acid-derived group and a drier power.
  • the emulsion resin is preferably a copolymer of ethylenically unsaturated monomers having a higher unsaturated fatty acid-derived group.
  • the aqueous curable antifouling coating composition is preferably such that the coating film obtained therefrom is used in water.
  • the aqueous binder component is preferably curable by acid-sodium polymerization.
  • the oxidative polymerization preferably involves a group derived from a higher unsaturated fatty acid.
  • the aqueous binder component is preferably an emulsion resin having a higher unsaturated fatty acid-derived group and a dryer power.
  • the emulsion resin is preferably a copolymer of ethylenically unsaturated monomers having a higher unsaturated fatty acid-derived group.
  • the aqueous curable antifouling paint composition of the present invention preferably further contains organic polymer particles.
  • the organic polymer particles described above have a solubility in artificial seawater stipulated in ASTM D1141-98 at 23 ° C of 15 gZL or less, and the water absorption of artificial seawater stipulated in ASTM D1141-98 is 0.01% by mass.
  • the particle size is preferably 0.05 to 100 / ⁇ ⁇ .
  • the organic polymer particles preferably have a cationic group.
  • the organic polymer particles have a particle size of 0.05-: LOO / zm and have at least one kind of organic polymer selected from the group consisting of chitin, chitosan, ⁇ -PGA, pulverized silk, and derivatives thereof. Preferred to be particles ,.
  • the organic polymer particles are preferably acrylic resin particles.
  • the organic polymer particles include starch, pullulan, arabianori, kappa lagerinan, gelatin, cellulose, chitosan and derivatives thereof, polybulal alcohol, polyallylamine, polybuluamine, poly (meth) acrylamide, poly (meth) It is preferred to be a composite resin particle comprising at least one hydrophilic resin selected from the group of (meth) acrylic acid and its copolymer power, and an acrylic resin.
  • the blending amount of the organic polymer particles is preferably 0.01 to 15% by mass with respect to the solid content of the paint.
  • the present invention is also an antifouling coating film characterized by being obtained by the above-mentioned aqueous curable antifouling coating composition.
  • This invention is also an underwater structure characterized by having the above-mentioned antifouling coating film.
  • the aqueous curable antifouling paint composition of the present invention comprises an aqueous binder component having curability and an antifouling agent.
  • the aqueous binder component contained in the aqueous curable antifouling coating composition of the present invention is not particularly limited as long as it has curability, and a solution in which water-soluble resin is dissolved, water-dispersible resin is used. It may consist of a dispersed resin in which the resin is forcibly dispersed with a dispersed emulsion resin, an emulsifier or the like. From the viewpoint of various performances such as water resistance and antifouling performance, it is particularly preferable to be made of an emulsion resin in which a water-dispersible resin is dispersed.
  • the emulsion resin contains a functional group for dispersing and emulsifying in water and a curing functional group.
  • the functional group for dispersing and emulsifying in water is not particularly limited, and examples thereof include basic groups such as acidic groups such as carboxyl groups and sulfonic acid groups, and amino groups.
  • the functional group for dispersing and emulsifying in water is an acidic group, it is more preferable that these acidic groups are contained within the range of 300 mgKOH / g or less as the acid value of the emulsion resin. Is 1-20 mg KOH / g.
  • As the acidic group a carboxyl group is particularly preferable.
  • a basic group it can be set in the same manner as an acidic group. Furthermore, it can be dispersed and emulsified in water by adding a polyethylene oxide unit. wear.
  • the functional group for dispersing and emulsifying in water is an acidic group
  • a base is added to the emulsion resin
  • the functional group for dispersing and emulsifying in water is a basic group
  • It can be dispersed and emulsified in water by adding an acid to the rosin rosin and neutralizing it.
  • the room temperature curability is preferably controlled by water or air.
  • Controlled by water or air means that the curing reaction proceeds by removing water by drying, or the curing reaction proceeds by contacting oxygen in the air by drying. It points to.
  • the aqueous binder component preferably has a property of being cured and decomposed by water.
  • the coating film obtained from the paint binder containing the water-based binder component is decomposed by being immersed in water, so that it exhibits self-polishing properties. it can.
  • Examples of the curing system having the property of decomposing with water include a dehydration condensation reaction. That is, in this case, the aqueous binder component is cured by dehydration condensation.
  • the dehydration condensation reaction is an equilibrium reaction that generates water
  • the curing reaction proceeds when water is removed by drying.
  • decomposition which is the reverse reaction of the curing reaction, proceeds due to the presence of a large amount of water.
  • the aqueous binder component may have a structure in which itself is cured, and a structure in which long-chain hydrocarbon groups are cross-linked with each other.
  • the antifouling agent tends to be eluted from the cured film obtained in the presence of the antifouling agent, which is preferable. This is thought to be because the structure in which the long-chain hydrocarbon groups are cross-linked has a looser and stronger network structure than the cross-linked structure obtained by other curing systems.
  • the long chain hydrocarbon groups are cross-linked.
  • structure means that an unsaturated bond of a long-chain hydrocarbon group and an unsaturated bond of another long-chain hydrocarbon group are directly or indirectly bonded. Examples of the indirect bond include a bond mediated by an oxygen atom in the following acid-polymerization reaction.
  • An oxidative polymerization reaction can be exemplified as the curing system that provides a structure in which the long-chain hydrocarbon groups are cross-linked.
  • the oxidative polymerization reaction is a reaction in which polymerization proceeds by absorbing oxygen into an unsaturated bond, and has a feature that it is excellent in quick-drying by using a dryer together.
  • an aqueous binder component that does not have the above-described characteristics such as a urethane curing system, there is a risk that the antifouling property for a long period is inferior.
  • examples of the curing system include canolebonino hydrazide, acetoacetamine, and anoleoxyxylinole condensation. These are known curing systems, and a combination of known greases and curing agents can be used.
  • the aqueous binder component has a carbo Z hydrazide-based curing system
  • the aqueous binder component is preferably composed of a carbonyl-containing resin and a hydrazide compound as a curing agent.
  • the carbonyl-containing resin is not particularly limited as long as it has at least one aldo group and Z or keto group.
  • Acrylic resin polyester resin (including alkyd resin), urethane resin Fats, epoxy greaves, their modified Z complex, etc.
  • acrylic resin is preferable in terms of points such as water resistance and physical properties of the coating film.
  • the carbonyl-containing resin is a carbonyl-containing acrylic resin, it is obtained by emulsion polymerization of a monomer composition containing an ethylenically unsaturated monomer containing an aldo group and a Z or keto group. It is preferable to use emulsion resin.
  • the ethylenically unsaturated monomer containing the aldo group and Z or keto group is not particularly limited, and examples thereof include acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene, vinyl methyl ketone, vinyl ester. Tyl ketone, vinyl isobutyl ketone, chloroalkyl alkyl panal, methacryloxy alkyl panal, diacetone acrylate, diacetone metatalylate, acetonyl acrylate, 2-hydroxy Examples include oral pill acetylate acetyl acetate, butanediol acrylate acetyl acetate, and the like.
  • the ethylenically unsaturated monomer containing the above aldo group and Z or keto group has an aldo group and Z or keto group in the obtained rosin of 0.005 to 20 mmolZ (resin solid content lg). It is preferable to use at a ratio of 0. If it is less than 05 mmol, curing reactivity will be insufficient and water resistance may not be sufficiently obtained. If it exceeds 20 mmol, other performance may be adversely affected.
  • the carbonyl-containing acrylic resin preferably has an acid value in the above-mentioned range.
  • the ethylenically unsaturated monomer having a carboxylic acid group is not particularly limited, and examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid; Saturated carboxylic acid anhydrides; half-esterified products of unsaturated carboxylic acids such as itaconic acid, fumaric acid and maleic acid.
  • the carbonyl-containing acrylic resin is neutralized with a base such as amine.
  • the neutralization rate is preferably 10 to 100%, more preferably 300% or less.
  • the carbonyl-containing acrylic resin preferably has a number average molecular weight of 3000 or more. If the number average molecular weight is less than 3000, the water resistance may decrease, which is not preferable.
  • the number average molecular weight is more preferably 10,000 or more.
  • the number average molecular weight can be appropriately adjusted to the target range by using a chain transfer agent, or by adjusting the polymerization initiator amount, polymerization temperature and the like to polymerize the resin.
  • the carbonyl-containing acrylic resin may use other monomers in addition to the above monomers.
  • the other monomers include ethylenically unsaturated monomers, and examples thereof include acrylic acid esters and methacrylic acid esters [hereinafter simply referred to as (meth) acrylic acid esters. ], Aromatic monomers such as styrene and butyltoluene, butyl esters such as butyl acetate, butyl propionate and butyl acid, cyano butyls such as (meth) acrylonitrile, butyl chloride, bis vinylidene, etc. Halogen Vinyl chloride, butadiene and the like.
  • acrylic acid ester or methacrylic acid ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methyl acrylate (meth) acrylate, (meth ) Cyclohexyl acrylate, dodecyl (meth) acrylate, and the like.
  • the carbo-containing resin is preferably emulsion resin as described above.
  • emulsion polymerization As means for obtaining emulsion resin, conventionally known emulsion polymerization is preferred. The reason is that the amount of functional groups to be introduced is easy to control and the molecular weight of the resin obtained by this method is relatively large. This is because it is possible to cope with the division.
  • a reactive emulsifier is used in the monomer composition, for example, in an aqueous medium containing water or an organic solvent such as alcohol if necessary. A method of emulsifying in advance and dropping this together with a polymerization initiator under heating and stirring can be exemplified.
  • the reactive emulsifier is not particularly limited, and may be any of eron type, cation type, noon type, and zwitterion type.
  • Examples of the reactive emulsifier include Elemiol JS series (manufactured by Sanyo Kasei Kogyo Co., Ltd.), Laterum S and Kashiwa series (manufactured by Kao Corporation), Aqualon HS series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap Series Commercial products such as (Asahi Denki Co., Ltd.) and Antstus MS-60 (Nippon Emulsifier Co., Ltd.) can be used.
  • the polymerization initiator is not particularly limited, and examples thereof include azobisisobutyl-tolyl, 2,2, -azobis (2-methylbutyoxy-tolyl), 2,2'-azobis (2,4-dimethylvale- G Ril) and other azo-based oil compounds, ⁇ ⁇ -on 4,4'-azobis (4-cyananovaleric acid), 2,2, -azobis (N- (2-carboxyethyl) 2-methylpropionamidine), etc.
  • Aqueous compounds such as redox oil peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauryl peroxide, t-butyl perbenzoate, potassium persulfate and ammonium persulfate.
  • redox oil peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauryl peroxide, t-butyl perbenzoate, potassium persulfate and ammonium persulfate.
  • An acid salt etc. can be mentioned.
  • the aqueous binder component When the aqueous binder component has the carbo Z hydrazide-based curing system, it contains a hydrazide compound as a curing agent.
  • the hydrazide compound is not particularly limited, and a compound having a plurality of hydrazide groups or semicarbazide groups can be used.
  • the compounds having a plurality of hydrazide groups in the molecule include oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, glutamic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, Dicarboxylic acid dihydrazide such as acid dihydrazide, Carbonic polyhydrazide such as carbonic dihydrazide, force Rubodihydrazide, thiocarbodihydrazide, 4, 4'-oxybenzenesulfonyl hydrazide, aliphatic, alicyclic, aromatic bissemicarbazide, aromatic Examples thereof include polymer hydrazides such as dicarboxylic acid hydrazide and polyacrylic acid hydrazide. Among these compounds, adipic acid dihydrazide is preferable.
  • the compound having a plurality of semicarbazide groups in the molecule is not particularly limited, and 1, 6-hexamethylenebis (N, N dimethylsemicarbazide), 1, 1, 1 ', 1'-tetramethyl 4, Examples thereof include semicarbazides such as 4 '-(methylene monodi (P) -phenylene) disemicarbazide and burette speed (hexamethylene-N, N dimethylsemicarbazide). These compounds may be used alone or in combination of two or more.
  • the water resistance is within the range of 6 to 1 to 0.1.
  • the aqueous binder component has a acetocetoxy-amine-based curing system
  • the aqueous binder component is preferably composed of a acetocetoxy group-containing resin and an amine compound as a curing agent.
  • the acetacetoxy group-containing resin is not particularly limited, but is preferably an acrylic resin, like the carbo-containing resin.
  • the above-mentioned acetocetoxy group-containing acrylic resin is not particularly limited, and examples thereof include a resin obtained by emulsion polymerization of a monomer composition containing an ethylenically unsaturated monomer containing a acetoacetoxy group. .
  • the ethylenically unsaturated monomer containing an acetoacetoxy group is not particularly limited, and examples thereof include acrylic acid esters and methacrylic acid esters having an acetoacetoxy group. Specific examples include acetatetoxetyl acetylate, acetatetoxetyl methacrylate and the like.
  • the acetacetoxy group-containing resin is preferably an emulsion resin, similar to the carbonyl-containing resin.
  • the polymerization method is not particularly limited, and for example, it can be obtained by the same method as the above-mentioned carbo-containing resin.
  • the amine compound is not particularly limited, and examples thereof include 2-methylpentamethylene diamine, cyclohexane diamine, hexamethylene diamine, ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 6-hexanediamine, 1,12-diaminododecane, 1,2-diaminocyclohexane, phenylenediamine, piperazine, 2,6-diaminotoluene, jetyltolueneamine, ⁇ , ⁇ -bis
  • Examples thereof include compounds having a diamine group or a polyamine group, such as (2-aminopropyl) ethylenediamine, ⁇ , ⁇ -bis (3-aminopropyl) -1,3-propanediamine.
  • the molar ratio between the amount of the curing functional group contained in the acetacetoxy group-containing resin and the amount of the curing agent functional group contained in the curing agent is preferably in the range of 1-10 to 1.05.05. If the molar ratio is out of the above range, the water resistance may decrease.
  • the molar ratio is more preferably in the range of I / O. 6 to lZ0.1 from the viewpoint of water resistance.
  • the water-based binder component is made of an alkoxysilyl group-containing resin.
  • the alkoxysilyl group is not particularly limited, and examples thereof include a methoxysilyl group and an ethoxysilyl group.
  • the alkoxysilyl group is regarded as a unit element constituting a functional group such as a dialkylmonoalkoxysilyl group, a monoalkyldialkoxysilyl group, a trialkoxysilyl group, and the like. Can do.
  • the alkoxysilyl group means a Si atom and one alkoxyl group bonded thereto.
  • a trialkoxysilyl group has three alkoxysilyl groups! /.
  • the alkoxysilyl group-containing resin is not particularly limited.
  • the ethylenically unsaturated monomer having an alkoxysilyl group is not particularly limited. For example, ⁇ -methacryloxypropyltrimethoxy silane, ⁇ -acryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropylmethylenedimethoxysilane , gamma - Atari b propyl dimethyl silane, .gamma.
  • methacryl Roxypropylmethyl jetoxysilane ⁇ -Atalyloxypropyl dimethylethoxysilane, ⁇ -Methacryloxypropyldimethylethoxysilane, Vinyltrimethoxysilane, Vinylmethyldimeth Shishiran, vinyltriethoxysilane, vinyl methyl diethoxy silane, trimethoxy silyl styrene, dimethoxy methyl silyl styrene, Torieto alkoxysilyl styrene, diethoxymethylsilyl styrene.
  • the alkoxysilyl group-containing resin is preferably an emulsion resin, similar to the carbo-containing resin.
  • the method for polymerizing the unsaturated monomer mixture is not particularly limited, and can be obtained, for example, by the same method as for the carbonyl-containing resin.
  • the aqueous binder component When the aqueous binder component has a curing system based on an alkoxysilyl condensation system, the aqueous binder component preferably further contains an acid and a salt or a base.
  • an acid and a base it does not specifically limit as said acid and a base,
  • a resin having a phosphate group is particularly preferable because of its high catalytic activity and the ease of introduction of a functional group that is preferable to a resin having a phosphate group or a sulfonate group.
  • the amino group is preferably a tertiary group in which two alkyl groups are bonded to a nitrogen atom.
  • the alkyl groups may be the same or different, but those having 1 to 8 carbon atoms are particularly preferable. Specific examples of such an amino group include a dimethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, a dioctylamino group, and the like.
  • the resin having the acid group or the basic group is not particularly limited. For example, by polymerization of a monomer composition containing an ethylenically unsaturated monomer having at least one acid group or basic group. What can be obtained can be mentioned.
  • the molar ratio of the amount of alkoxysilyl group contained in the alkoxysilyl-containing resin to the acid and / or base is preferably in the range of 1Z10 to 1Z0.001. If the molar ratio exceeds 1ZO.01, the curability becomes insufficient and the water resistance may be lowered. If the molar ratio is less than lZio, the amount of unreacted acid and Z or base increases, and the water resistance may decrease.
  • the above-mentioned molar ratio is preferably in the range of 1Z0.6 to lZ0.1.
  • a carbo-hydrazide system is preferable because of good self-polishing properties due to the progress of the reverse reaction of the curing reaction, and among them, the curing reactivity is excellent.
  • Carbon / semicarbazide combination is particularly preferred ⁇
  • a group derived from a higher unsaturated fatty acid is preferably involved. This is because the unsaturated bond in the group derived from a higher unsaturated fatty acid undergoes acid-polymerization, thereby obtaining the structure in which the long-chain hydrocarbon groups described above are cross-linked.
  • Examples of the resin having a group derived from a higher unsaturated fatty acid include alkyd resin, and acrylic emulsion resin is preferable.
  • Acrylic emulsion resin having a group derived from a higher unsaturated fatty acid is obtained by emulsion polymerization of a monomer composition containing an ethylenically unsaturated monomer having a higher unsaturated fatty acid derived group. Obtainable.
  • the ethylenically unsaturated monomer having a group derived from a higher unsaturated fatty acid is not particularly limited, and may be obtained, for example, by a reaction between a higher unsaturated fatty acid and a glycidyl group-containing ethylenically unsaturated monomer.
  • the higher unsaturated fatty acid is not particularly limited, and examples thereof include myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid.
  • non-conjugated double bonds such as linseed oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, eno oil fatty acid, hemp oil fatty acid, cottonseed oil fatty acid, tall fatty acid, etc.
  • examples thereof include dry oil fatty acids and semi-dry oil fatty acids.
  • some fatty acids having a conjugated double bond such as tung oil fatty acid can be used in combination.
  • the average carbon number of the hydrocarbon portion of the higher unsaturated fatty acid is preferably 13-23.
  • the iodine value of the ethylenically unsaturated monomer having a group derived from a higher unsaturated fatty acid is preferably 60 to 180, more preferably 70 to 150! /.
  • the polymerization method of the emulsion resin having a group derived from a higher unsaturated fatty acid is not particularly limited, and can be obtained, for example, by the same method as the carbonyl-containing resin. Moreover, it is preferable that the iodine value of the emulsion resin which has the said higher unsaturated fatty acid origin group is 5-100. If the iodine value exceeds 100, the surface of the coating film is dried quickly, so that a sufficient effect cannot be obtained.
  • the aqueous binder component When the aqueous binder component has a curing system by oxidative polymerization reaction, it preferably further contains a dryer.
  • the dryer functions to crosslink the unsaturated bond of the higher unsaturated fatty acid-derived group.
  • the dryer is not particularly limited as long as it is usually used for paints, but, among others, cobalt, vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, cerium, nickel, and tin Naphthenate, octylate, succinate, etc. it can.
  • the amount of the dryer is usually 0.005 to 5 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the aqueous binder component is also preferably one that cures at room temperature by an addition reaction.
  • a curing system is not particularly limited, and examples thereof include a urethane Z urea system, a nickel addition system, and a calpositimide Z carboxyl system.
  • the urethane Z urea system is not particularly limited, and examples thereof include an aqueous binder component comprising a polyisocyanate compound as a curing agent and a hydroxyl group and Z or amino group-containing resin.
  • an aqueous binder component comprising a polyisocyanate compound as a curing agent and a hydroxyl group and Z or amino group-containing resin.
  • acrylic resin As the above-mentioned hydroxyl group and Z or amino group-containing resin, acrylic resin
  • Polyester resin urethane resin, polyether resin, polycarbonate resin and the like, and those well known to those skilled in the art can be used.
  • the polyisocyanate compound is not particularly limited, and examples thereof include tolylene diisocyanate 1 HTDI), 4, 4, 1-diphenylmethane diisocyanate (MDI), xylylene diisocyanate.
  • Aromatic diisocyanate compounds such as cyanate (XDI); hexamethylene diisocyanate (H MDI), isophorone diisocyanate (IPDI), 2, 5— or 2, 6-bis ( Aliphatic or alicyclic diisocyanate compounds such as isocyanatomethyl) bicyclo [2, 2, 1] heptane (norbornane diisocyanate NBDI); or two of these diisocyanate compounds Mention may be made of polyisocyanate compounds such as trimers, trimers and trimethylolpropane adducts.
  • the blocking agent is not particularly limited.
  • aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethylhexanol, ethylene glycol monobutyl ether, cyclohexanol; phenol, nitrophenol, ethylphenol, etc. phenols; Mechiruechiruketo Okishimu such as Okishimu; epsilon can be given Ratatamu, and the like, such as one force Puroratatamu.
  • the molar ratio of the amount of the curing functional group contained in the hydroxyl group-containing resin or amino group-containing resin to the amount of the curing agent functional group contained in the polyisocyanate compound is 1/10 to 1 / 0.05. It is preferable to be within the range. When the molar ratio exceeds 1ZO. 05, the curability becomes insufficient and the water resistance may be lowered. If the molar ratio is less than 1 to 10, the amount of unreacted polyisocyanate compound increases, and the water resistance may be lowered. Above mole The ratio is more preferably in the range of 1Z0.6 to 1Z0.1, in terms of water resistance.
  • the calpositimide-carboxyl system is not particularly limited, and examples thereof include a carboxyl group-containing resin containing a carboxyl group as a curing functional group, and an aqueous binder component comprising a polycarbodiimide compound as a curing agent. Can do.
  • the carboxyl group-containing resin is not particularly limited, and examples thereof include a carboxyl group-containing acrylic resin, a carboxyl group-containing polyester resin, a carboxyl group-containing alkyl resin, and a carboxyl group-containing polyurethane resin. be able to.
  • the carboxyl group-containing resin is an acrylic resin, an emulsion obtained by emulsion polymerization of a monomer composition containing an ethylenically unsaturated monomer containing a rupoxyl group containing acrylic acid and methacrylic acid. It is preferable to use rosin.
  • polycarposimide compound commercially available products such as V-02 manufactured by Nisshinbo Industries, Inc. can be used.
  • polyisocyanate compound listed above is known as a carbopositimide catalyst, and is carbodiimidized using phosphoroxide to obtain an isocyanate-terminated polycarbopositimide, which is used for hydrophilicity.
  • carbopositimide catalyst commercially available products
  • phosphoroxide phosphoroxide
  • isocyanate-terminated polycarbopositimide which is used for hydrophilicity.
  • the molar ratio between the amount of the curing functional group contained in the carboxyl group-containing resin and the amount of the curing agent functional group contained in the polycarposimide compound is in the range of 1 to 10 to 1.0 to 0.05. Is preferred. If the molar ratio exceeds 1ZO. 05, the water resistance may decrease. If the molar ratio is less than 1 to 10, the water resistance may decrease. The above molar ratio is more preferably in the range of I / O. 6 to lZ0.1, from the viewpoint of water resistance.
  • the Michael addition system is not particularly limited.
  • an aqueous binder component composed of a compound having an active methylene group and a cocoon or an active methine group and a compound having a, j8-unsaturated carbonyl group. Can be mentioned.
  • Examples of the compound having an active methylene group and Z or an active methine group include acetoacetic acid, malonic acid, cyanoacetic acid, and derivatives thereof.
  • the derivative is not particularly limited, and examples thereof include a reaction product of a polyol and the above compound.
  • the compound having a plurality of a, j8-unsaturated carbonyl groups is not particularly limited.
  • those having two or more metatalylate groups and Z or attalylate groups per molecule for example, a with respect to a carbonyl group, a metatallate group having a double bond between ⁇ -carbon, and two or more ⁇ or attalylate groups And the like.
  • Specific examples include (meth) acrylic acid esters of polyols, such as ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol propane pantri (meth) acrylate.
  • the molar ratio between the amount of the cured functional group contained in the compound having the active methylene group and the cocoon or active methine group and the unsaturated bond contained in the compound having a plurality of the ⁇ , ⁇ unsaturated carbonyl groups is , Preferably in the range of 1 ⁇ 10 to 1 ⁇ .05.
  • the molar ratio exceeds 1 / 0.05 the curability becomes insufficient and the water resistance may be lowered.
  • the molar ratio is less than 1Z10, the amount of the compound having a plurality of unreacted ⁇ , ⁇ unsaturated carbonyl groups increases, and the water resistance may be lowered.
  • the above molar ratio is more preferably in the range of 1ZO. 6 to I / O. 1 from the viewpoint of water resistance.
  • the aqueous curable antifouling paint composition of the present invention further contains an antifouling agent.
  • the antifouling agent is not particularly limited, and known ones can be used, and examples thereof include inorganic compounds, organic compounds containing metals, and organic compounds containing no metals.
  • the antifouling agent is not particularly limited, and examples thereof include cuprous oxide, Manganese ethylene bis dithiocarbamate, zinc dimethinorecarbamate, 2-methinorethio 4-tobutinoreamino 1-cyclopropylamino 1 s triazine.
  • the blending amount of the antifouling agent is preferably 0.1% by mass as the lower limit and 80% by mass as the upper limit in the solid content of the coating. If the amount is less than 1% by mass, the antifouling effect cannot be expected. If the amount exceeds 80% by mass, defects such as cracks and peeling may occur in the coating film.
  • the blending amount is more preferably a lower limit of 1% by mass and an upper limit of 60% by mass.
  • the antifouling agent may be blended as an antifouling agent paste comprising a water-soluble dispersion resin and the antifouling agent.
  • an antifouling agent paste By using such an antifouling agent paste, it becomes easy to release the antifouling agent in water, and excellent antifouling properties can be obtained.
  • a water-soluble binder component that does not have the above-mentioned characteristics such as urethane curing system, it is preferable to use the above antifouling paste.
  • the antifouling agent paste is used together with a curable aqueous binder component, so that the resulting coating film becomes a cured film, so that the water resistance is excellent. It has excellent antifouling properties. This is considered to be because when the coating film is used in water, the antifouling agent is likely to be eluted by the water-soluble disperse resin contained in the antifouling agent paste.
  • the water-soluble dispersed resin is not particularly limited, and known dispersed resins such as acrylic resin, polyester resin, urethane resin can be used, but the acid value is 10 to 300 mg KOH Zg, The number average molecular weight is preferably in the range of 1000-20000. [0079] If the acid value is less than lOmgKOHZg, the water solubility is lowered and the stability is impaired. On the other hand, when the acid value exceeds 300 mgKOHZg, the hydrophilicity of the resin is too high, and the water resistance of the coating film may be lowered. The upper limit is more preferably lOOmgKOHZg.
  • the number average molecular weight is less than 1000, the molecular weight is too low and the antifouling agent may not be sufficiently dispersed. On the other hand, when the number average molecular weight exceeds 20000, water solubility may not be ensured, or the viscosity becomes too high and handling may be difficult.
  • the lower limit is more preferably 5000, and the upper limit is 15000, which is more preferable than the force S.
  • the mixing ratio of the water-soluble dispersion resin and the antifouling agent is preferably in the range of 1Z99 to 50Z50 in terms of solid content. If the mixing ratio is out of the range, the dispersion viscosity of the antifouling agent paste may become too high, or the dispersibility of the antifouling agent may decrease, resulting in insufficient stability.
  • the pigment content is preferably 50% by mass or less.
  • the antifouling paste is, for example, a sand grinder containing the water-soluble dispersion resin and the antifouling agent. It can be obtained by a method of mixing using a pigment disperser such as a der mill.
  • the antifouling paste is blended so that the blending amount of the antifouling agent in the water-based antifouling coating composition is within the range of 0.1% by mass of the lower limit and 80% by mass of the upper limit in the solid content of the paint. I prefer to do it.
  • the amount is less than 0.1% by mass, the antifouling effect cannot be expected, and when it exceeds 80% by mass, defects such as cracks and peeling may occur in the coating film. More preferably, the lower limit is 1% by mass and the upper limit is 60% by mass.
  • the aqueous curable antifouling coating composition of the present invention preferably further contains organic polymer particles.
  • the organic polymer particles can be easily formed into a coating film having low friction performance by being added as an additive to the aqueous curable antifouling coating composition of the present invention! It is what has.
  • the organic polymer particles have a solubility in artificial seawater specified by ASTM D1141-98 at 23 ° C of 15 gZL or less, and the water absorption of artificial seawater specified by ASTM D1141-98 is 0. 01 mass% or more, particle size 0.05-: LOO / zm In other words, regardless of the chemical structure of the polymer, when organic polymer particles satisfying the above properties are added, desired physical properties can be obtained.
  • the organic polymer particles preferably have a solubility in artificial seawater as defined in ASTM D1141-98 at 23 ° C of 15 gZL or less. If the solubility exceeds 15 gZL, sufficient low friction performance may not be exhibited. Preferably, the solubility is 12 gZL or less.
  • the above-mentioned solubility is a value obtained by measuring the solubility of the organic polymer particles in artificial seawater prepared according to ASTM D1141-98 after weighing under reduced pressure at room temperature and weighing.
  • the organic polymer particles preferably have an artificial seawater absorption amount of 0.01% by mass or more as defined in ASTM D1141-98. If the water absorption is less than 0.01% by mass, the affinity with seawater is low, so that a sufficient effect cannot be obtained, and the reduction of friction is suppressed. Book Since the organic polymer particles used in the invention swell when contacted with water and do not dissolve in water, the organic polymer particles preferably exhibit low friction performance. It is possible. Preferably, the water absorption amount is 0.1% by mass or more.
  • the water absorption amount in the present invention was precisely weighed in an organic polymer particle lg dried under vacuum (under reduced pressure) at room temperature and added to 50 g of artificial seawater prepared according to ASTM D 1141-98. Thereafter, the mixture was stirred at 23 ° C. for 5 hours, and then filtered, and the residue was washed with water and weighed.
  • the organic polymer particles preferably have a particle size in a range of 0.05 ⁇ m as a lower limit and 100 ⁇ m as an upper limit. If the particle size is less than 0.05 / zm, a sufficient friction reducing effect cannot be obtained. When the particle size exceeds 100 m, there is a possibility that the surface condition of the coating film is deteriorated.
  • the lower limit is preferably 0.1 m
  • the upper limit is preferably 40. More preferably, it is 1-30 / ⁇ ⁇ .
  • the above particle diameter is measured under the following conditions, and refers to the average value of the particle diameters that are output when the distribution standard described in the following device manual is set as volume.
  • Dispersion medium for measurement deionized water
  • the organic polymer particle may be a naturally-derived polymer or a synthetic polymer.
  • the organic polymer particles preferably have an appropriate amount of hydrophilic functional group and, if necessary, have a crosslinked chain.
  • the hydrophilic functional group include a hydroxyl group, an amino group, a carboxy group, an amide group, and a polyoxyethylene group.
  • Naturally-derived polymers that can be used as the organic polymer particles of the present invention include, for example, chitin, chitosan, gum arabic, alginic acid, carrageenan, agar, chitansan gum, dielan gum, cellulose, xylose, starch, Examples include polysaccharides such as pullulan, pectin, roasted bean gum, dextran, and curdlan; proteins such as keratin, collagen, silk, and ⁇ -polyglutamic acid (hereinafter referred to as ⁇ -PGA): nucleic acids.
  • hydrolysis, crosslinking reaction, etc. are performed on these naturally derived polymers as necessary.
  • derivatives such as hydroalkylation), polyethylene glycolation, hydrophobization (eg alkylation), grafting, and three-dimensional semi-synthetic polymers are also included.
  • the naturally derived polymer preferably has a cationic group.
  • a cationic group By having a cationic group, the effect of reducing the friction of the coating film in seawater can be more easily obtained.
  • the force thione group is not particularly limited, and examples thereof include an amino group, an amide group, and a pyridine group.
  • Natural polymers that originally have a cationic group may be used, and in the case of a polymer that does not have a cationic group, a cationic group may be introduced by derivatizing the polymer. Good.
  • the organic polymer particles are more preferably at least one organic polymer particle selected from the group consisting of chitin, chitosan, ⁇ -PGA, pulverized silk, and derivatives thereof.
  • the chitin is a polysaccharide, and this deacetylated product is chitosan.
  • the deacetylated cocoon may be completely deacetylated or partially deacetylated. If necessary, it may be modified or crosslinked with polyoxyethylene, an aldehyde group-containing compound, or the like.
  • the silk pulverized product is obtained by pulverizing silk, which is an eyebrow produced by silkworms, into particles.
  • the silk pulverized product used in the present invention is a product obtained by pulverizing natural silk as it is, and then pulverizing it by removing miscellaneous components, hydrolysis, purification, classification, etc. as necessary. It's okay.
  • ⁇ PGA has the following general formula (1);
  • [0101] is a polymer represented by Familiar materials are the main ingredients of the stickiness produced by Bacillus natto, and are polymers that are disliked as polymeric absorbent materials, biodegradable materials, medical materials, food additives, and cosmetic materials.
  • the ⁇ -PGA particles used in the present invention are those obtained by drying and granulating naturally-derived ones produced by the above fungi.
  • the ⁇ -PGA particles may be made into particles by removing miscellaneous components, hydrolyzing, purifying, and classifying as necessary.
  • a synthetic polymer may be used as the organic polymer particle.
  • the synthetic polymer is not particularly limited, and examples thereof include acrylic resin, polyester resin, amine-based resin, and modified polyvinyl alcohol-based resin. These are preferably hydrophilic resins having a hydrophilic group such as a hydroxyl group, an amino group, or a carboxyl group, and may have a partially crosslinked structure as necessary.
  • Organic polymer particles can be obtained by adjusting the hydrophilic Z hydrophobicity and the crosslinking ratio by a known method.
  • acrylic resin particles can be preferably used as the synthetic polymer.
  • the acrylic resin particles can be obtained, for example, by emulsion polymerization of a monomer composition comprising an acrylic monomer and a crosslinkable monomer.
  • the acrylic monomer is not particularly limited.
  • ethylenically unsaturated monomers may be used.
  • the ethylenically unsaturated monomer is not particularly limited, and examples thereof include styrene, ⁇ -methyl styrene, butyltoluene, t-butylstyrene, butyl acetate, butyl propionate and the like.
  • the acrylic monomer and ethylenically unsaturated monomer may be used alone or in combination of two or more.
  • the crosslinkable monomer is not particularly limited.
  • two or more radicals are included in the molecule.
  • examples thereof include a monomer having a polymerizable ethylenically unsaturated bond.
  • the monomer having two or more radically polymerizable ethylenically unsaturated bonds in the molecule that can be used in the production of the acrylic resin particles is not particularly limited.
  • the crosslinkable monomer is preferably 1% by mass or more based on the total amount of the monomer composition. If the mass ratio is out of the above range, the desired talyl-based resin particles may not be obtained. The mass ratio is more preferably 5 to 70% by mass.
  • the polymerization method of the monomer composition is not particularly limited, and can be performed by a conventionally known method such as emulsion polymerization or suspension polymerization.
  • the organic polymer particles may be composite resin particles having two or more kinds of polymer power.
  • the composite resin particles having two or more kinds of polymer forces referred to here are particles of two or more of the above-mentioned various naturally-derived polymers and synthetic polymers.
  • the specific means is not particularly limited, and examples thereof include arbitrary methods such as mixing, grafting, core-shelling, IPN (internet network invasion structure), and surface treatment.
  • the two or more types of polymers are not particularly limited, and examples thereof include the above-mentioned naturally-derived polymers and the above-described synthetic polymers. Among them, starch, pullulan, arabianori, kappa laginin, gelatin, cellulose, chitosan and their derivatives, polybulal alcohol, polyallylamine, polybuluamine, poly (meth) acrylamide, poly (meth) acrylic acid and its derivatives It is preferably a composite resin particle comprising at least one hydrophilic resin selected from the group consisting of copolymer power and acrylic resin. Such a combination is preferable in that hydrophilicity can be obtained while changing the physical properties of the particles as desired by the composition of the acrylic resin.
  • the hydrophilic and acrylic resins may be used by combining those that cannot achieve the object of the present invention alone.
  • the hydrophilic resin it is more preferable to use at least one resin selected from chitosan, chitosan derivatives, and polybutyl alcohol.
  • the composite resin particles comprising the hydrophilic resin and the acrylic resin for example, emulsion polymerization or suspension polymerization of the raw material monomer of the acrylic resin in the presence of the hydrophilic resin.
  • emulsifier used during the polymerization a known emulsifier can be used, but a reactive emulsifier is preferable from the viewpoint of water resistance. Examples of the reactive emulsifier include those mentioned above.
  • the amount of the reactive emulsifier added is preferably 15% by mass or less. If it exceeds 15% by mass, the water resistance of the coating film obtained from the coating powder containing the composite resin particles may be lowered.
  • the mixing ratio of the monomer composition that is the raw material of the acrylic resin and the hydrophilic resin is preferably 40Z60 to 97Z3 in terms of mass ratio (solid content).
  • the blending amount of the organic polymer particles in the coating composition of the present invention is preferably in the range of 0.01% by mass lower limit and 15% by mass upper limit with respect to the total solid content in the coating. the above If the blending amount is less than 0.01% by mass, the desired effect cannot be obtained, which is not preferable. If the blending amount exceeds 15% by mass, the friction reduction effect in water corresponding to the blending amount may not be obtained.
  • the lower limit is more preferably 0.1% by mass, and the upper limit is more preferably 12% by mass.
  • the aqueous curable antifouling paint composition of the present invention may contain one or more of the above organic polymer particles.
  • a coating film having excellent low friction performance in addition to water resistance and antifouling property by applying the aqueous curable antifouling coating composition containing the organic polymer particles described above to the surface of the object to be coated. Can be formed.
  • the aqueous curable antifouling coating composition of the present invention containing the organic polymer particles described above when applied to a ship traveling at a speed of about 10 to 30 knots, good low friction performance can be imparted. it can.
  • the coating composition By applying the coating composition, it is possible to reduce the frictional resistance by 2 to 3% or more compared to the conventional antifouling coating.
  • the coating composition of the present invention in which the organic polymer particles are blended can significantly contribute to the reduction of navigation fuel consumption, particularly as a ship bottom coating.
  • the water-based curable antifouling coating composition of the present invention may contain conventional additives such as plasticizers and pigments in addition to the above-described components.
  • plasticizer examples include phthalate ester plasticizers such as dioctyl phthalate, dimethyl phthalate, and dicyclohexyl phthalate; aliphatic dibasic ester plasticizers such as isobutyl adipate and dibutyl sebacate; diethylene glycol dibenzo Glycol ester plasticizers such as phosphates and pentaerythritol alkyl esters; phosphate ester plasticizers such as tritarenediphosphoric acid and trichlorodiethylphosphoric acid; epoxy plasticizers such as epoxy soybean oil and oxyethyl stearate; And organic tin plasticizers such as octyltin laurate and dibutylbutyl laurate; trioctyl trimellitic acid, triacetylene and the like. These may be used alone or in combination of two or more.
  • Examples of the pigment include extender pigments such as precipitated barium, talc, clay, chalk, silica white, alumina white and bentonite; acid titanium, acid zircon, basic lead sulfate, tin oxide , Carbon black, graphite, bengara, chrome yellow, phthalocyanine glue And coloring pigments such as quinone, phthalocyanine blue and quinacridone. These may be used alone or in combination of two or more.
  • extender pigments such as precipitated barium, talc, clay, chalk, silica white, alumina white and bentonite
  • acid titanium, acid zircon basic lead sulfate, tin oxide , Carbon black, graphite, bengara, chrome yellow
  • coloring pigments such as quinone, phthalocyanine blue and quinacridone.
  • additives are not particularly limited.
  • monobasic organic acids such as monobutyl phthalate and monooctyl succinate, camphor, etc .
  • water binder, sagging agent prevention of color separation Agents; anti-settling agents; antifoaming agents and the like.
  • the method for preparing the water-based curable antifouling paint composition of the present invention is not particularly limited. These conventional additives can be added and mixed using a mixer such as a ball mill, pebble mill, roll mill, sand grind mill, or the like.
  • a mixer such as a ball mill, pebble mill, roll mill, sand grind mill, or the like.
  • an antifouling agent as an antifouling paste
  • the antifouling agent and the water-soluble dispersion resin, and further, a pigment, a plasticizer, and other additives are mixed in advance using a sand grinder mill, etc.
  • the above-mentioned coating composition can be prepared by mixing with an aqueous binder component and organic polymer particles.
  • the aqueous curable antifouling coating composition preferably has a nonvolatile content of 10 to 90 mass%. If the non-volatile content is less than 10% by mass, thick film formation may be difficult. If the non-volatile content exceeds 90% by mass, it may be difficult to adjust the viscosity during coating.
  • the aqueous curable antifouling coating composition preferably has a PWC of 50 to 90% by mass.
  • the room temperature drying property may decrease.
  • the PWC exceeds 90% by mass, film formation may be difficult.
  • the aqueous curable antifouling coating composition is capable of forming a dry coating film by applying water to the surface of an article to be coated according to a conventional method and then stripping off water at ordinary temperature. .
  • the coating film thus obtained has an effect of suppressing contamination of the underwater structure.
  • An antifouling coating film obtained by applying the aqueous curable antifouling coating composition is one aspect of the present invention, and an underwater structure having the antifouling coating film is also one aspect of the present invention. .
  • the antifouling coating film is formed, for example, by applying the aqueous curable antifouling coating composition by a conventionally known method such as dipping, spraying, brushing, roller, electrostatic coating or the like. can do. After coating, leave it to dry at room temperature, or strong at about 80 ° C Anti-drying may be performed for several hours to about 1 day.
  • the dry film thickness of the antifouling coating film is preferably in the range of a lower limit of 30 ⁇ m and an upper limit of 500 / zm. It is preferable that the dry film thickness is in the above range because the balance between water resistance and antifouling property is good.
  • the mass ratio of the resin solid content to the antifouling agent in the antifouling coating film is not particularly limited, but is preferably 1: 7 to 1: 1 from the viewpoint of the antifouling effect.
  • the amount of the curing functional group contained in the antifouling coating film is within the range of 0.00015 to 8 mmolZg with respect to the resin solid content.
  • the point of water resistance and antifouling property is preferable. Note that the amount of the cured functional group can also be used to calculate the paint compounding power.
  • the article to be coated may be pretreated as necessary.
  • the material to be coated is not particularly limited, and is preferably an underwater structure because it forms a coating film exhibiting excellent low friction performance.
  • the underwater structure is not particularly limited, and examples thereof include ships, piping materials, fishing nets and the like.
  • the water-based curable antifouling coating composition of the present invention can provide a coating film having excellent water resistance and a good antifouling effect.
  • an aqueous curable antifouling coating composition capable of forming a coating film excellent in water resistance and having a good antifouling effect could be obtained. Since the antifouling coating film obtained by the water-based curable antifouling coating composition has the above-described effects, it can be widely applied to underwater structures.
  • a reaction vessel equipped with a dropping funnel, thermometer, nitrogen inlet tube, reflux condenser and stirrer was charged with 2 parts of Aqualon HS-10 in 70 parts of ion exchanged water and heated to 80 ° C under a nitrogen atmosphere. Warm up. Next, the obtained pre-emulsion and the aqueous initiator solution were simultaneously added dropwise from a separate dropping funnel over 3 hours. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchanged water and 1 part of dimethylethanolamine.
  • the carboxylic group-containing emulsion resin thus obtained had a solid content of 40% by mass and an average particle size of 90 nm.
  • Acetacetoxy group-containing emulsion resin was obtained in the same manner as in Production Example 1 except that 10 parts of diacetone acrylamide was changed to 10 parts of acetatetoxetyl methacrylate.
  • the obtained acetoacetoxy group-containing emulsion resin had a solid content of 40% and an average particle size of 90 nm.
  • An alkoxysilyl group-containing emulsion resin was obtained in the same manner as in Production Example 1, except that 10 parts of diacetone acrylamide was changed to 10 parts of KBM-503 (methacryloxyprobitrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.). The resulting alkoxysilyl group-containing emulsion resin is
  • the solid content was 40% and the average particle size was 90 nm.
  • the obtained higher unsaturated fatty acid-derived group-containing emulsion resin had a solid content of 40% and an average particle size of 90 nm.
  • the antifouling agent By adding 20 parts of deionized water, 40 parts of cuprous oxide, 5 parts of zinc pyrithione, 5 parts of zinc white, 5 parts of Bengala, 5 parts of talc, and BYK-190 as a pigment dispersant (manufactured by Bicchemi) By adding 20 parts and BYK-019 (produced by Big Chemi Co., Ltd.) as an antifoaming agent and dispersing with a sand grinder, the antifouling agent has a solid content of 76.5% by mass, PWC92% and a particle size of 20 / zm. Got a strike.
  • Carbon fiber-containing emulsion resin obtained in Production Example 1 100 parts, Hardener SC (Asahi Kasei Corporation semicarbazide curing agent, solid content 50 mass%) 4 parts, Antifouling agent paste obtained in Production Example 5 200 3 parts of PUR-2150 (Axo's Nobel Urethane Associative Thickener, solid content 35% by mass) were dispersed with a disperser to obtain an aqueous curable antifouling paint composition.
  • This coating composition has a PWC of 72%, a solid content of 64% by mass, a curing functional group amount of Z-carbonyl group: 0.12 mmol / g, a semicarbazide group: 0.047 mmolZg, and an acid value of 1. OmgKOHZg.
  • the viscosity of the coating composition was adjusted with ion-exchanged water so that the viscosity with a Steam Viscometer at 25 ° C was 90KU.
  • FRP plate (100 X 300) which was roughened with sandpaper (grain size 240).
  • a test coated plate was obtained by leaving it in an atmosphere at a temperature of 20 ° C and a relative humidity of 65% for 1 day.
  • Acetacetoxy group-containing emulsion resin obtained in Production Examples 2, 3, and 4 alkoxysilyl group-containing emulsion resin, higher unsaturated fatty acid-derived group-containing emulsion resin, and Watersol 3060 (Dainippon Ink Chemical Co., Ltd.) Aqueous alkyd oil)
  • Aqueous curable antifouling paint composition was prepared in the same manner as in Example 1 except that Bihydrol A145 (a polyol for waterborne polyurethane manufactured by Sumika Bayer Urethane Co., Ltd.) was used and the composition was changed to the composition shown in Table 1. Obtained. Further, a test coated plate was obtained in the same manner as in Example 1.
  • a comparative water-based non-curable antifouling coating composition was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1, and a test coated plate was obtained.
  • test coating plate was dripped in the seawater lm at a sea depth of lm at Okayama Prefecture Tamano Kaoru and Nippon Paint Marine Co., Ltd., and the surface condition of the coating film was observed visually after 1, 6 and 12 months. The results are shown in Table 1.
  • the water resistance was evaluated according to the following criteria.
  • Antifouling property was evaluated according to the following criteria.
  • X 10% or more and less than 50% of test plate area has animals and plants
  • test plate area At least 50% of test plate area is attached to animals and plants
  • the resulting water-based curable antifouling paint composition was evaluated for self-polishing properties by the following method.
  • aqueous curable antifouling paint composition was coated on an FRP plate (with gel coat treatment) roughened with sandpaper (particle size 240) with an applicator so that the dry film thickness was about 240 m. After painting, leave it in an atmosphere at a temperature of 20 ° C and a relative humidity of 65% for one day.
  • a test coated plate was obtained. This test coating plate was attached to a rotating drum installed in seawater, rotated at a peripheral speed of 10 knots, and the consumable film thickness m) was measured every 3 months. The results are shown in Table 1.
  • Example 1 using a carbonyl Z hydrazide system as a curing system was excellent in antifouling property. The appearance of this antifouling property is thought to be related to self-polishing properties.
  • a monomer mixture consisting of 10 parts of soybean oil fatty acid adduct of glycidyl metatalylate, 30 parts of methyl methacrylate, 20 parts of ethyl acrylate, 30 parts of n-butyl acrylate, 9 parts of styrene and 1 part of methacrylic acid is ionized.
  • the monomer mixture was emulsified using a stirrer. The pre-emulsion was obtained. Further, 0.3 part of ammonium persulfate was dissolved in 17 parts of ion-exchanged water to obtain an aqueous initiator solution.
  • a reaction vessel equipped with a dropping funnel, thermometer, nitrogen inlet tube, reflux condenser and stirrer was charged with 70 parts of ion exchanged water and 2 parts of Aqualon HS-10, and the temperature was raised to 80 ° C under a nitrogen atmosphere. Warm up. Next, the obtained pre-emulsion and the aqueous initiator solution were simultaneously added dropwise from a separate dropping funnel over 3 hours. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchanged water and 1 part of dimethylethanolamine. The resulting higher unsaturated fatty acid-derived group-containing emulsion resin had a solid content of 40% and an average particle size of 90 nm.
  • Methyl methacrylate 36 parts, Ethyl acrylate 20 parts, N-butyl acrylate 30 parts, Styrene 10 parts, Methacrylic acid 10 parts HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.-based reactive emulsifier) is added to the solution obtained by mixing, and then emulsified with a stirrer to pre-emulsion the monomer mixture. Obtained.
  • 0.3 part of ammonium persulfate was dissolved in 17 parts of ion-exchanged water to obtain an initiator aqueous solution.
  • a reaction vessel equipped with a dropping funnel, thermometer, nitrogen inlet tube, reflux condenser and stirrer was charged with 70 parts of ion exchanged water and 2 parts of Aqualon HS-10, and the temperature was raised to 80 ° C under a nitrogen atmosphere. Warm up. Next, the obtained pre-emulsion and the aqueous initiator solution were simultaneously added dropwise from a separate dropping funnel over 3 hours. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchanged water and 1 part of dimethylethanolamine.
  • the obtained carboxyl group-containing emulsion resin has a solid content of 40% and an average particle size of 40%.
  • test coated plate was obtained by leaving it in an atmosphere at a temperature of 20 ° C and a relative humidity of 65% for 1 day. Further, a test coated plate was obtained in the same manner as in the example.
  • test coating board Water resistance and antifouling property were evaluated by the method similar to the method mentioned above except having made immersion period 1 month and 6 months. The results are shown in Table 2.
  • Example 7 of a curing system based on an acid-polymerization system is used to cure other addition polymerizations. Antifouling property was superior to the system.
  • Comparative Examples 2 and 3 which did not use an antifouling paste, had no problem with water resistance, but the antifouling property was inferior, and Comparative Example 4, which was non-cured, had problems with water resistance. It became clear.
  • Chitin (made by Dainichi Seika Co., Ltd .: Chitin P) and chitosan (Kyoyo Chemical Co., Ltd .: SK-10) were each pulverized with a jet crusher, and organic polymer particles C with a particle size of 7 m and a chitin force were also obtained.
  • organic polymer particles D having a particle size of 8 ⁇ m and having a chitosan force were obtained.
  • Chitosan (“Daichitosan VL", NV 100%, manufactured by Dainichi Seiya Kogyo Co., Ltd.) 7. Og, ion-exchanged water 57.7 7g, and acrylic acid 5.3g were mixed with a stirrer to obtain a chitosan aqueous solution. This chitosan aqueous solution 70. Og, ER-20 (Non-one reactive emulsifier manufactured by Asahi Denki Co., Ltd.) 30. Og and ions To an aqueous solution consisting of 162.6 g of exchange water, 28.8 g of methyl methacrylate, 10.
  • PEO Polyethylene oxide
  • PEO-1 Polyethylene oxide (PEO-1) (“PEO-1”, NV100%, manufactured by Sumitomo Seika Co., Ltd.) 7.
  • PEO aqueous solution was obtained by mixing 57.7 g of Ogion exchange water with a stirrer. This aqueous PEO solution 64.7 g, ER-20 30.0 g and ion-exchanged water 162.6 g were added to an aqueous solution of 42.
  • a stirrer A turbid liquid (suspended particle size 34 ⁇ m) was obtained.
  • the organic polymer particles lg dried under vacuum (under reduced pressure) at room temperature were precisely weighed and added to 50 g of artificial seawater prepared according to ASTM D1141-988, followed by stirring at 23 ° C for 5 hours. Thereafter, the mixture was filtered, and the residue was washed with water and weighed to determine the amount of water absorption.
  • An aqueous curable antifouling coating composition was obtained by sequentially adding the blending components shown in Table 3, the antifouling agent paste of Production Example 5 and organic polymer particles, and dispersing them with a disperser. Next, the viscosity of the obtained antifouling coating composition was adjusted with ion-exchanged water so that the viscosity with a steam viscometer at 25 ° C was 90 KU. The unit of the blending amount in Table 3 is “g”. For organic polymer particles E and F, each organic polymer particle dispersion was added.
  • This antifouling coating composition was applied to an FRP plate (100 X 3 00 X 3mm, with gel coat treatment) roughened with sandpaper (grain size 240) with a brush so that the dry film thickness was 00 ⁇ m. Painted. After coating, a test coated plate was obtained by leaving it in an atmosphere at a temperature of 20 ° C and a relative humidity of 65% for 1 day.
  • the resulting aqueous curable antifouling coating composition was evaluated for a frictional resistance test by the following method.
  • the coating film formed by the paint obtained in the example shows excellent low friction performance in addition to excellent water resistance and antifouling property, and the effect is maintained for a long time. I knew that. Moreover, the state of the coating film surface was also favorable.
  • the aqueous curable antifouling paint composition of the present invention comprises a curable aqueous binder component and an antifouling agent, and thus forms a coating film having excellent water resistance and good antifouling effect.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de revêtement à l'épreuve des taches hydraulique comprenant un composant liant aqueux ayant une propriété de durcissement et un agent antitaches, laquelle peut donner un film de revêtement applicable à l'utilisation sous l'eau. Comme composant liant, on peut utiliser au moins un système de durcissement sélectionné entre un système carbonyle/hydrazide, un système acétoacétoxy/amine et un système de condensation d'alcoxysilyles ; un agent de durcissement et une résine en émulsion ayant un groupe réactif avec un groupe fonctionnel présent dans l'agent de durcissement ; ou similaire. L'invention concerne un agent antitaches pâteux comprenant une résine en dispersion soluble dans l'eau ayant un indice d'acidité de 10 à 300 mg de KOH/g et un poids moléculaire moyen en nombre de 1000 à 20000 et un agent antitaches ; une composition de revêtement à l'épreuve des taches hydraulique comprenant un composant liant aqueux ayant une propriété de durcissement ; un film de revêtement à l'épreuve des taches formé à partir de la composition de revêtement à l'épreuve des taches hydraulique ; une structure immergée sous l'eau ayant le film de revêtement à l'épreuve des taches.
PCT/JP2005/024116 2004-12-28 2005-12-28 Composition de revêtement à l'épreuve des taches hydraulique, film de revêtement à l'épreuve des taches et structure immergée sous l'eau WO2006077738A1 (fr)

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CN2005800452760A CN101094899B (zh) 2004-12-28 2005-12-28 水性固化型防污涂料组合物、防污性涂膜及水中结构物
GB0712694A GB2435602B (en) 2004-12-28 2005-12-28 Hydraulic stain-proof coating composition, stain-proof coating film and underwater structure

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JP2004379674A JP2006182956A (ja) 2004-12-28 2004-12-28 防汚剤ペーストを含む水性硬化型防汚塗料組成物
JP2004-379674 2004-12-28
JP2004379673A JP2006182955A (ja) 2004-12-28 2004-12-28 水性硬化型防汚塗料組成物、防汚性塗膜及び水中構造物
JP2005368799A JP2007169449A (ja) 2005-12-21 2005-12-21 水性硬化型防汚塗料組成物、防汚性塗膜、水中構造物及び水中摩擦低減方法
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Cited By (8)

* Cited by examiner, † Cited by third party
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CN101180960A (zh) * 2007-11-07 2008-05-21 上海木村生物科技有限公司 渔网防藻剂及其制备方法
WO2009084191A1 (fr) * 2007-12-28 2009-07-09 Toto Ltd. Matériau composite comportant un film de revêtement soluble de manière progressive et une composition de revêtement
KR100936451B1 (ko) 2008-12-05 2010-01-13 도요 잉키 세이조 가부시끼가이샤 활성 에너지선 경화성 조성물
WO2010141981A1 (fr) * 2009-06-09 2010-12-16 Duluxgroup (Australia) Pty Ltd Durcisseur pour peinture
EP2468825A1 (fr) 2010-12-21 2012-06-27 Akzo Nobel Coatings International B.V. Composition de revêtement antisalissure
WO2012150360A2 (fr) 2011-12-02 2012-11-08 Akzo Nobel Coatings International B.V. Composition de revêtement antisalissure à base d'eau
WO2015146748A1 (fr) * 2014-03-27 2015-10-01 日本ペイント株式会社 Composition aqueuse de revêtement durcissable à la température ambiante
WO2018012381A1 (fr) * 2016-07-11 2018-01-18 株式会社クラレ Composition de revêtement pour repousser des organismes aquatiques

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TWI440673B (zh) * 2008-09-30 2014-06-11 Nippon Paint Co Ltd Coating composition and method for producing the same, coating film and water structure
KR101372312B1 (ko) * 2012-05-22 2014-03-12 주식회사 홍서이엔씨 수중 콘크리트 조성물 및 그에 의해 제조된 인공어초
JP6139969B2 (ja) * 2013-05-13 2017-05-31 アイカ工業株式会社 水系塗材組成物
CN108368381B (zh) * 2015-12-11 2021-04-16 中国涂料株式会社 用于形成降低摩擦阻力的涂膜的涂料组合物、涂膜和带涂膜的基材
KR102385401B1 (ko) * 2017-09-26 2022-04-08 다우 글로벌 테크놀로지스 엘엘씨 수성 중합체 조성물

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JPS6136376A (ja) * 1984-07-27 1986-02-21 Nippon Paint Co Ltd プレコ−トメタル用塗料組成物
JPS6230164A (ja) * 1985-04-18 1987-02-09 Nippon Paint Co Ltd ポリシング型防汚塗料組成物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101180960A (zh) * 2007-11-07 2008-05-21 上海木村生物科技有限公司 渔网防藻剂及其制备方法
WO2009084191A1 (fr) * 2007-12-28 2009-07-09 Toto Ltd. Matériau composite comportant un film de revêtement soluble de manière progressive et une composition de revêtement
KR100936451B1 (ko) 2008-12-05 2010-01-13 도요 잉키 세이조 가부시끼가이샤 활성 에너지선 경화성 조성물
WO2010141981A1 (fr) * 2009-06-09 2010-12-16 Duluxgroup (Australia) Pty Ltd Durcisseur pour peinture
US9133347B2 (en) 2010-12-21 2015-09-15 Akzo Nobel Coatings International B.V. Antifouling coating composition
EP2468825A1 (fr) 2010-12-21 2012-06-27 Akzo Nobel Coatings International B.V. Composition de revêtement antisalissure
WO2012084758A1 (fr) 2010-12-21 2012-06-28 Akzo Nobel Coatings International B.V. Composition de revêtement antisalissure
WO2012150360A2 (fr) 2011-12-02 2012-11-08 Akzo Nobel Coatings International B.V. Composition de revêtement antisalissure à base d'eau
US9290669B2 (en) 2011-12-02 2016-03-22 Akzo Nobel Coatings International B.V. Waterborne antifouling coating composition
WO2015146748A1 (fr) * 2014-03-27 2015-10-01 日本ペイント株式会社 Composition aqueuse de revêtement durcissable à la température ambiante
JP2015193779A (ja) * 2014-03-27 2015-11-05 日本ペイント株式会社 常温硬化型水性塗料組成物
WO2018012381A1 (fr) * 2016-07-11 2018-01-18 株式会社クラレ Composition de revêtement pour repousser des organismes aquatiques
JPWO2018012381A1 (ja) * 2016-07-11 2019-05-16 株式会社クラレ 水生生物忌避用塗料組成物
US10829661B2 (en) 2016-07-11 2020-11-10 Kuraray Co., Ltd. Aquatic organism repellent paint composition

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