WO2011125179A1 - 防汚塗料組成物、防汚塗膜の製造方法、および防汚塗膜 - Google Patents
防汚塗料組成物、防汚塗膜の製造方法、および防汚塗膜 Download PDFInfo
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- WO2011125179A1 WO2011125179A1 PCT/JP2010/056251 JP2010056251W WO2011125179A1 WO 2011125179 A1 WO2011125179 A1 WO 2011125179A1 JP 2010056251 W JP2010056251 W JP 2010056251W WO 2011125179 A1 WO2011125179 A1 WO 2011125179A1
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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
- 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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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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
- 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
- C09D5/1668—Vinyl-type polymers
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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
- 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 antifouling paint composition and an antifouling coating film.
- Anti-fouling paint is applied to the flooded parts of ships and offshore structures to prevent corrosion due to adhesion of marine organisms such as barnacles, snails, and algae, and to prevent a reduction in ship navigation speed.
- an antifouling paint is applied to prevent clogging of the net due to adhesion of marine organisms.
- Such antifouling paints include organic tin, and have a self-polishing property that develops long-term antifouling properties by gradually dissolving the coating surface and constantly exposing the antifouling component to the coating surface.
- Dirty paint was known.
- organic tin is used as an antifouling paint, organic tin eluted in seawater affects fish and shellfish, and therefore, development of a paint having self-polishing properties that does not use organic tin is being promoted.
- Patent Document 1 describes an antifouling coating composition containing an acrylic polymer having a metal ester structure such as Mg, Zn, or Cu.
- Patent Document 2 includes an acrylic resin varnish having a metal ester structure in the side chain, a nonvolatile content of 40% by mass or more, a viscosity at 25 ° C. of 18 poise or less, and an organic solvent content of 400 g / l or less. The paint is described.
- the antifouling paint composition described in Patent Document 1 has a high viscosity of the acrylic polymer, it has been necessary to dilute it to a viscosity suitable for coating using a large amount of an organic solvent. For this reason, it took time to dry the coating film.
- the coating film formed with the antifouling paint described in Patent Document 2 has a problem that the molecular weight is low and the coating film strength is low.
- the present invention provides an antifouling coating composition that can form a coating film that has a small amount of organic solvent used to form a coating film, maintains strength and self-polishing properties for a long period of time, and exhibits excellent antifouling properties.
- the purpose is to provide.
- Another object of the present invention is to provide an antifouling coating film that maintains strength and self-polishing properties for a long period of time and exhibits excellent antifouling properties and a method for producing the same.
- the first gist of the present invention is an antifouling coating composition containing an acrylic polymer (P), a radical polymerizable monomer (M), and an organic peroxide (O), the acrylic polymer (P) and At least one of the radically polymerizable monomers (M) is in the antifouling coating composition having a divalent metal ester structure.
- the second gist of the present invention is that the organic antifouling coating composition containing the acrylic polymer (P), the radical polymerizable monomer (M), and the organic peroxide (O) is applied to the substrate.
- a method for producing an antifouling coating film comprising a step of decomposing a peroxide (O), wherein at least one of the acrylic polymer (P) and the radical polymerizable monomer (M) has a divalent metal ester structure. is there.
- the third gist of the present invention resides in an antifouling coating film obtained by the above method for producing an antifouling coating film.
- the amount of the organic solvent used when forming the coating film can be reduced, and a coating film that maintains strength and self-polishing properties for a long period of time and exhibits excellent antifouling properties can be obtained.
- the antifouling coating composition of the present invention contains an acrylic polymer (P), a radical polymerizable monomer (M), and an organic peroxide (O). Since the antifouling coating composition of the present invention contains the radical polymerizable monomer (M), even when the viscosity of the acrylic polymer (P) is high, the viscosity is suitable for coating without using a large amount of organic solvent. Can be adjusted. Further, even when the molecular weight of the acrylic polymer (P) is low, the coating film formed using the antifouling coating composition of the present invention is polymerized with the radical polymerizable monomer (M) by the organic peroxide (O). Thus, the strength of the coating film can be maintained.
- P acrylic polymer
- M radical polymerizable monomer
- O organic peroxide
- At least one of the acrylic polymer (P) and the radical polymerizable monomer (M) has a divalent metal ester structure.
- the polymer with a bivalent metal ester structure exists in the coating film obtained from the antifouling coating composition of the present invention.
- a coating film shows self-polishing property because the bivalent metal ester structure of this polymer hydrolyzes in seawater.
- the antifouling component is always exposed on the surface of the coating film, and a long-term antifouling effect is exhibited.
- the acrylic polymer (P) preferably has a divalent metal ester structure in that the solubility of the formed coating film is increased, and both the acrylic polymer (P) and the radical polymerizable monomer (M) It is more preferable that has a divalent metal ester structure.
- the divalent metal constituting the divalent metal ester structure is preferably magnesium (Mg), zinc (Zn), or copper (Cu).
- the acrylic polymer (P) is a polymer obtained by homopolymerizing or copolymerizing the (meth) acrylic monomer (Ma).
- the (meth) acrylic monomer (Ma) may have one (meth) acryloyl group, may have two or more (meth) acryloyl groups, and in addition to the (meth) acryloyl group It may have other radical polymerizable functional groups.
- a non-acrylic monomer (Mb) can also be used as a monomer copolymerized with the (meth) acrylic monomer (Ma).
- the acrylic polymer (P) has a divalent metal ester structure (hereinafter, this polymer is also referred to as “metal-containing acrylic polymer (Pm)”)
- the (meth) acrylic monomer (Ma) is divalent.
- a (meth) acrylic monomer (Mc) having a metal ester structure (hereinafter also referred to as “metal-containing acrylic monomer (Mc)”) is used, or 2 as a monomer copolymerized with the (meth) acrylic monomer (Ma).
- a non-acrylic monomer (Md) having a valent metal ester structure hereinafter also referred to as “metal-containing non-acrylic monomer (Md)” may be used.
- At least a part of the (meth) acrylic acid unit may be esterified using a divalent metal oxide, hydroxide or salt.
- the polymer obtained by copolymerizing a metal containing acrylic monomer (Mc) is preferable.
- the acrylic polymer (P) can be used in combination of two or more.
- Acrylic acid ester monomer Adducts of hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate with ethylene oxide, propylene oxide, ⁇ -butyrolactone or ⁇ -caprolactone; Dimer or trimer of hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid ester monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate; Primary and secondary amino group-containing (meth) acrylic acid ester monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide; Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoprop
- (meth) acrylic monomer (Ma) other than the metal-containing acrylic monomer (Mc) it is possible to adjust the solubility in seawater and the coating film hardness.
- methyl (meth) acrylate or ethyl (meth) acrylate is preferable.
- non-acrylic monomer (Mb) other than the metal-containing non-acrylic monomer (Md) Heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; Vinyl monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, (meth) acrylonitrile, vinyl acetate, vinyl propionate; Is mentioned.
- Two or more non-acrylic monomers (Mb) other than the metal-containing non-acrylic monomer (Md) can be used in combination.
- the metal-containing acrylic monomer (Mc) is preferably a di (meth) acrylic acid metal ester monomer.
- a di (meth) acrylic acid metal ester monomer By using a di (meth) acrylic acid metal ester monomer, the coating strength is significantly improved by taking a three-dimensionally crosslinked structure of the polymer, and the divalent metal ester structure is hydrolyzed stably in seawater. A long-term antifouling effect due to dissolution of the surface of the coating film is effectively exhibited.
- the amount of the monomer used is preferably 1 to 60 parts by mass and more preferably 5 to 50 parts by mass with respect to a total of 100 parts by mass of the copolymerized monomers. More preferred is 10 to 40 parts by mass.
- the metal-containing acrylic polymer (Pm) may be a polymer obtained by homopolymerizing or copolymerizing (meth) acrylic acid and then esterifying with a divalent metal oxide, hydroxide or salt.
- a polymer obtained by copolymerizing a metal-containing acrylic monomer (Mc) and a metal-free acrylic monomer is preferable.
- esters A polymer obtained by copolymerizing 50 parts by mass or more of a (meth) acrylic monomer having 1 to 4 carbon atoms with respect to a total of 100 parts by mass of copolymerization monomers is preferred. Since this polymer has a relatively high solubility in seawater, a long-term antifouling effect due to dissolution of the surface of the coating film is effectively exhibited.
- the acid value of the acrylic polymer (P) is preferably 25 mgKOH / g or more.
- An acid value here means the acid value with respect to solid content of an acrylic polymer (P). This includes not only the case where hydrogen is bonded to the terminal of the acid group in the acrylic polymer (P) but also the case where it is a metal salt.
- the acid value of the acrylic polymer (P) can be determined by calculation or by acid value measurement described below.
- the acid value of the acrylic polymer (P) is more preferably 40 mgKOH / g or more, and most preferably 60 mgKOH / g or more, from the viewpoint of developing good solubility.
- the content of the carboxyl group (expressed by —COOH, excluding the case where it is a metal salt) in the acrylic polymer (P) is preferably 1.5 mol / kg or less, more preferably 0.3 mol / kg or less. preferable. If content of the carboxyl group in acrylic polymer (P) is 1.5 mol / kg or less, the water resistance of a coating film will become good and storage stability will also become favorable. Content of the carboxyl group in acrylic polymer (P) is calculated
- the weight average molecular weight of the acrylic polymer (P) is preferably 30,000 or less, more preferably 15,000 or less, and even more preferably 7,000 or less.
- the weight average molecular weight of the acrylic polymer (P) is 30,000 or less, the viscosity as a coating is lowered, and it is easy to obtain a high solid type.
- acrylic polymer (Pm) has good hydrolyzability and can be applied to antifouling paints.
- radically polymerizable monomer (M) As the radically polymerizable monomer (M), the above-mentioned (meth) acrylic monomer (Ma) or non-acrylic monomer (Mb) can be used.
- the radical polymerizable monomer (M) only an acrylic monomer (Ma) other than the metal-containing acrylic monomer (Mc) can be used, or only the metal-containing acrylic monomer (Mc) can be used. Is preferred.
- the amount of the metal-containing acrylic monomer (Mc) used is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, with respect to 100 parts by weight of the radical polymerizable monomer (M). More preferred is 70 parts by weight.
- the blending ratio of the acrylic polymer (P) and the radical polymerizable monomer (M) can be appropriately selected according to the polymerizability of the radical polymerizable monomer (M).
- the mass ratio of acrylic polymer (P) / radically polymerizable monomer (M) is preferably 30/70 to 95/5, more preferably 50/50 to 90/10, and 60/40 to 85/15. Further preferred.
- the mass of acrylic polymer (P) here is the mass of polymer solids excluding the organic solvent.
- the amount of metal contained in the total mass of the acrylic polymer (P) and the radical polymerizable monomer (M) is preferably 2 to 40% by mass, more preferably 3 to 30% by mass, and even more preferably 4 to 25% by mass. When the amount of metal is 2% by mass or more, good self-polishing properties can be obtained. When the amount of metal is 40% or less, cracking of the obtained coating film is difficult to occur.
- the mass of acrylic polymer (P) here is the mass of polymer solids excluding the organic solvent.
- Organic peroxide (O) is an organic compound having an —O—O— bond, and generates a free radical by decomposition. By this free radical, the radical polymerizable monomer (M) undergoes radical polymerization.
- Hydroperoxides such as diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; Di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl Dialkyl peroxides such as peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diisobutyryl peroxide, di (3,5,5-trimethylhexanonyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, di (3
- the blending amount of the organic peroxide (O) can be appropriately selected according to the curability of the radical polymerizable monomer (M).
- the acrylic polymer (P) The total amount of the radically polymerizable monomer (M) and the solvent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 6 parts by mass.
- the blending amount of the organic oxide (O) is 0.1 parts by mass or more, the curability tends to be good, and when it is 10 parts by mass or less, the coating workability of the antifouling paint composition is increased. The various physical properties of the resulting coating film tend to be improved.
- Decomposition accelerator (A) In the antifouling coating composition, it is preferable to incorporate a decomposition accelerator (A) in order to accelerate the decomposition of the organic peroxide (O).
- a decomposition accelerator (A) By the action of the decomposition accelerator (A), the organic peroxide (O) is decomposed at room temperature (for example, 20 ° C.), and the radical polymerization monomer (M) can be promoted to undergo radical polymerization.
- N N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-diethylaniline, N- (2-hydroxyethyl) -N-methyl-p-toluidine, N, N-bis ( N, N-substitution such as 2-hydroxyethyl) -p-toluidine or its ethylene oxide or propylene oxide adduct, N, N-bis (2-hydroxypropyl) -p-toluidine or its ethylene oxide or propylene oxide adduct -P-toluidine; 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, etc.
- N 4- (N, N-substituted amino) benzaldehyde; N, N-dimethylanily , N, N- bis (hydroxyethyl) aniline, N, such as diethanol aniline, N- substituted aromatic tertiary amines such as aniline; Other amines such as aniline, p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine; Thiourea compounds such as methylthiourea, diethylthiourea, acetylthiourea, tetramethylthiourea, ethylenethiourea; Metal salts such as cobalt naphthenate, copper naphthenate, manganese naphthenate, nickel naphthenate, vanadyl acetylacetonate, titanium acetylacetonate; Is mentioned.
- aromatic tertiary amines are preferred.
- aromatic tertiary amine those in which at least one aromatic residue is directly bonded to the nitrogen atom are preferable.
- aromatic tertiary amines include N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-diethylaniline, N- (2-hydroxyethyl) N-methyl- p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl) -p-toluidine; N, N-bis (2-hydroxyethyl) -p- Mention may be made of toluidine or N, N-bis (2-hydroxypropyl) -p-toluidine ethylene oxide or propylene oxide adducts.
- the aromatic tertiary amine is not limited to the p (para) isomer, and may be an o (ortho) isomer or an m (meth) isomer.
- N, N -Dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl) -p-toluidine are preferred .
- the amount of amine added as the decomposition accelerator (A) is such that the solid content of the acrylic polymer (P) and the monomer content of the radical polymerizable monomer (M) are from the viewpoint of balance between curability and pot life (workability).
- the total content is preferably from 0.01 to 10 parts by weight, more preferably from 0.1 to 8 parts by weight, particularly preferably from 0.2 to 6 parts by weight, based on a total of 100 parts by weight.
- the addition amount of the thiourea compound or the metal salt as the decomposition accelerator (A) is 0. 0 with respect to 100 parts by mass in total of the solid content of the acrylic polymer (P) and the pure monomer content of the radical polymerizable monomer (M). 01 to 5 parts by mass is preferable, and 0.1 to 4 parts by mass is more preferable.
- the decomposition accelerator may be added immediately before the antifouling paint composition is cured, or may be added in advance to the antifouling paint composition.
- the addition amount of the organic peroxide (O) and the decomposition accelerator (A) is preferably adjusted as appropriate so that the pot life of the antifouling coating composition is 5 to 120 minutes.
- a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or 2,4-dimethyl-t-butylphenol can be added.
- an antifouling agent in the antifouling coating composition, can be blended according to the required performance.
- Antifouling agents include copper antifouling agents such as cuprous oxide, thiocyanic copper and copper powder, other metal compounds such as lead, zinc and nickel, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds and maleimides Compounds, pyridine compounds, and the like.
- a transition metal compound such as cuprous oxide when used as an antifouling agent, curing proceeds even without adding a decomposition accelerator (A).
- This is considered to function as a decomposition accelerator by the action of at least one of the acrylic polymer (P) and the radical polymerizable monomer (M) and the divalent metal ester. Therefore, it is preferable to use a transition metal compound such as cuprous oxide as an antifouling agent in terms of supplementing the function of the decomposition accelerator (A).
- Antifouling agents can be used in combination of two or more.
- the blending amount of the antifouling agent can be appropriately selected according to the intended antifouling property.
- the solid content of the acrylic polymer (P) and the radical polymerizable monomer 0.1 to 500 parts by mass is preferable and 5 to 350 parts by mass is more preferable with respect to 100 parts by mass of the total amount of pure monomer M).
- a wax (C) having a melting point of 40 ° C. or higher can be blended for the purpose of suppressing the effect of inhibiting the polymerization of oxygen on the surface of the coating film and improving water resistance.
- the wax (C) include higher fatty acids such as paraffin wax, polyethylene wax, and stearic acid, and two or more kinds having different melting points can be used in combination.
- the amount of the wax (C) used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the solid content of the acrylic polymer (P) and the pure monomer of the radical polymerizable monomer (M). 2 to 2 parts by mass is more preferable. Use of a large amount of the wax (C) may impair the appearance of the coating film surface.
- Antifouling paint composition is formulated with silicone compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbon, etc. for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms. can do. Furthermore, extender pigments, color pigments, plasticizers, various paint additives, other resins, and the like can be blended in the antifouling paint composition as necessary.
- the antifouling paint composition can be used as an antifouling paint after being diluted with an organic solvent as necessary.
- the antifouling coating film of the present invention is an organic antifouling coating composition in which an antifouling coating composition containing an acrylic polymer (P), a radical polymerizable monomer (M) and an organic peroxide (O) is applied to a substrate. It can be obtained by decomposing the oxide (O). At this time, at least one of the acrylic polymer (P) and the radical polymerizable monomer (M) has a divalent metal ester structure. Specifically, an antifouling paint containing the aforementioned antifouling paint composition is applied to a substrate to be coated, and a coating film obtained at a temperature higher than the decomposition temperature of the organic peroxide (O) is obtained.
- An antifouling coating film can be obtained by drying and polymerizing the radical polymerizable monomer (M) by decomposition of the organic peroxide (O).
- the decomposition temperature of the organic peroxide (O) is lower than room temperature, it can be dried at room temperature.
- the decomposition accelerator (A) is added, it can be dried at a decomposition temperature or lower as long as the decomposition of the organic peroxide (O) occurs.
- the antifouling coating composition is preferably mixed immediately before coating.
- the mixing method a method of preparing an acrylic polymer (P) / radically polymerizable monomer (M) mixture and adding an organic peroxide (O) immediately before coating is preferable.
- the acrylic polymer (P) may be mixed with a radical polymerizable monomer (M) / organic peroxide (O) mixture, or the radical polymerizable monomer (M) may be mixed with an acrylic polymer (P) / organic. You may mix a peroxide (O) mixture.
- the acrylic polymer (P) and the radical polymerizable monomer (M) are preferably mixed with a solvent, but the acrylic polymer (P) may be a powder.
- the surface of the substrate such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base is used.
- the base material coated with wash primer, chlorinated rubber-based, epoxy-based primer, intermediate coating, etc. on the base material by means of brush coating, spray coating, roller coating, submersion coating, etc. can do.
- the coating amount is generally set so that the thickness of the dried coating film is 50 to 400 ⁇ m.
- the coating film is generally dried at room temperature, but may be heat-dried.
- part means “part by mass”
- % means “% by mass”.
- the acid value (mgKOH / g) of the acrylic polymer (P) the mass of potassium hydroxide required to neutralize 1 g of the solid content of the acrylic polymer was measured.
- the weight average molecular weight of the acrylic polymer (P) is GPC (manufactured by Tosoh Corporation, HLC-8120GPC (trade name), Tosoh Corporation column TSK-gel, ⁇ type ( ⁇ -M), 2 eluent: dimethylformamide).
- GPC manufactured by Tosoh Corporation, HLC-8120GPC (trade name), Tosoh Corporation column TSK-gel, ⁇ type ( ⁇ -M), 2 eluent: dimethylformamide).
- Table 1 shows the composition and physical properties of the acrylic polymer (P).
- Examples 1 to 13, Comparative Examples 1 and 2 The radically polymerizable monomer (M) and the acrylic polymer (P) were mixed at the blending ratio shown in Table 2. Thereafter, at the blending ratio shown in Table 2, a decomposition accelerator is added at 20 ° C., followed by addition of an organic peroxide (O), so that the theoretical solid content of the coating becomes 50-60%.
- a coating composition was prepared.
- the theoretical solid content means a mass ratio of the radical polymerizable monomer (M) and the acrylic polymer (P) contained in the antifouling coating composition.
- the obtained antifouling coating composition was quickly applied onto a predetermined substrate and dried at room temperature for 48 hours to obtain a coating film having a dry film thickness of about 180 ⁇ m. The following measurements and evaluations were made on the antifouling paint composition and the coating film.
- Viscosity of antifouling paint composition Viscosity of the antifouling paint composition was measured using a B type viscometer. Measurements were made using 2-4 rotors. The results are shown in Table 2.
- the antifouling paint compositions obtained in Examples 1 to 13 were able to achieve a viscosity suitable for coating even when the solid content was 50% or more. Moreover, it was excellent in water resistance in seawater, self-polishing, cross-cut peel test (adhesion) was good, and antifouling property was also good.
- Comparative Example 1 containing no radical polymerizable monomer (M) had extremely high viscosity and was difficult to be applied to a high solid type of paint.
- Comparative Example 2 which does not contain an acrylic polymer (P) had a low viscosity, both the cross-cut peel test and the water resistance were low.
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Abstract
Description
本発明の防汚塗料組成物は、アクリルポリマー(P)、ラジカル重合性モノマー(M)、および有機過酸化物(O)を含有する。本発明の防汚塗料組成物中はラジカル重合性モノマー(M)を含んでいるので、アクリルポリマー(P)の粘度が高い場合でも、多量の有機溶剤を使用することなく塗装に適した粘度に調整することができる。また、アクリルポリマー(P)の分子量が低い場合であっても、本発明の防汚塗料組成物を用いて形成した塗膜は有機過酸化物(O)によってラジカル重合性モノマー(M)が重合して得られるポリマーを含むことになるため、塗膜の強度が維持できる。
アクリルポリマー(P)は(メタ)アクリル系モノマー(Ma)を単独重合または共重合して得られるポリマーである。(メタ)アクリル系モノマー(Ma)は、1つの(メタ)アクリロイル基を有していてもよく、2つ以上の(メタ)アクリロイル基を有していてもよく、(メタ)アクリロイル基以外に他のラジカル重合性官能基を有していてもよい。(メタ)アクリル系モノマー(Ma)と共重合するモノマーとしては、非アクリル系モノマー(Mb)も使用できる。
(メタ)アクリル酸;
メチル(メタ)アクリレート、エチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、2-(2-エチルヘキサオキシ)エチル(メタ)アクリレート、1-メチル-2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、3-メチル-3-メトキシブチル(メタ)アクリレート、m-メトキシフェニル(メタ)アクリレート、p-メトキシフェニル(メタ)アクリレート、o-メトキシフェニルエチル(メタ)アクリレート、m-メトキシフェニルエチル(メタ)アクリレート、p-メトキシフェニルエチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、i-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、t-アミル(メタ)アクリレート、n-オクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ミリスチル(メタ)アクリレート、パルミチル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、グリシジル(メタ)アクリレート、トリフルオロエチル(メタ)アクリレート、パーフルオロオクチル(メタ)アクリレート、γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン、γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン等の(メタ)アクリル酸エステルモノマー;
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステルモノマー;
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステルモノマーと、エチレンオキサイド、プロピレンオキサイド、γ-ブチロラクトンまたはε-カプロラクトン等との付加物;
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステルモノマーの二量体または三量体;
グリセロール(メタ)アクリレート等の水酸基を複数有する(メタ)アクリル酸エステルモノマー;
ブチルアミノエチル(メタ)アクリレート、(メタ)アクリルアミド等の第一級および第二級アミノ基含有(メタ)アクリル酸エステルモノマー;
ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、ジメチルアミノブチル(メタ)アクリレート、ジブチルアミノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリルアミド、ジメチルアミノプロピル(メタ)アクリルアミド等の第三級アミノ基含有(メタ)アクリル酸エステルモノマー;
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、1,2-プロピレングリコールジ(メタ)アクリレート、1,3-プロピレングリコールジ(メタ)アクリレート、1,3-ブチレングリコールジ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、アリル(メタ)アクリレート等の多官能(メタ)アクリル酸エステルモノマー;
が挙げられる。金属含有アクリルモノマー(Mc)以外の(メタ)アクリル系モノマー(Ma)は、2種以上を組み合わせて用いることもできる。
ビニルピロリドン、ビニルピリジン、ビニルカルバゾール等の複素環族系塩基性単量体;
スチレン、ビニルトルエン、α-メチルスチレン、(メタ)アクリロニトリル、酢酸ビニル、プロピオン酸ビニル等のビニル系単量体;
が挙げられる。金属含有非アクリルモノマー(Md)以外の非アクリル系モノマー(Mb)は、2種以上を組み合わせて用いることもできる。
酢酸マグネシウム(メタ)アクリレート、酢酸亜鉛(メタ)アクリレート、酢酸銅(メタ)アクリレート、モノクロル酢酸マグネシウム(メタ)アクリレート、モノクロル酢酸亜鉛(メタ)アクリレート、モノクロル酢酸銅(メタ)アクリレート、モノフルオロ酢酸マグネシウム(メタ)アクリレート、モノフルオロ酢酸亜鉛(メタ)アクリレート、モノフルオロ酢酸銅(メタ)アクリレート、プロピオン酸マグネシウム(メタ)アクリレート、プロピオン酸亜鉛(メタ)アクリレート、プロピオン酸銅(メタ)アクリレート、カプロン酸マグネシウム(メタ)アクリレート、カプロン酸亜鉛(メタ)アクリレート、カプロン酸銅(メタ)アクリレート、カプリル酸マグネシウム(メタ)アクリレート、カプリル酸亜鉛(メタ)アクリレート、カプリル酸銅(メタ)アクリレート、2-エチルヘキシル酸マグネシウム(メタ)アクリレート、2-エチルヘキシル酸亜鉛(メタ)アクリレート、2-エチルヘキシル酸銅(メタ)アクリレート、カプリン酸マグネシウム(メタ)アクリレート、カプリン酸亜鉛(メタ)アクリレート、カプリン酸銅(メタ)アクリレート、バーサチック酸マグネシウム(メタ)アクリレート、バーサチック酸亜鉛(メタ)アクリレート、バーサチック酸銅(メタ)アクリレート、イソステアリン酸マグネシウム(メタ)アクリレート、イソステアリン酸亜鉛(メタ)アクリレート、イソステアリン酸銅(メタ)アクリレート、パルミチン酸マグネシウム(メタ)アクリレート、パルミチン酸亜鉛(メタ)アクリレート、パルミチン酸銅(メタ)アクリレート、クレソチン酸マグネシウム(メタ)アクリレート、クレソチン酸亜鉛(メタ)アクリレート、クレソチン酸銅(メタ)アクリレート等の飽和脂肪族カルボン酸(メタ)アクリル酸金属エステルモノマー;安息香酸マグネシウム(メタ)アクリレート、安息香酸亜鉛(メタ)アクリレート、安息香酸銅(メタ)アクリレート、2,4,5-トリクロロフェノキシ酢酸マグネシウム(メタ)アクリレート、2,4,5-トリクロロフェノキシ酢酸亜鉛(メタ)アクリレート、2,4,5-トリクロロフェノキシ酢酸銅(メタ)アクリレート、2,4-ジクロロフェノキシ酢酸マグネシウム(メタ)アクリレート、2,4-ジクロロフェノキシ酢酸亜鉛(メタ)アクリレート、2,4-ジクロロフェノキシ酢酸銅(メタ)アクリレート、キノリンカルボン酸マグネシウム(メタ)アクリレート、キノリンカルボン酸亜鉛(メタ)アクリレート、キノリンカルボン酸銅(メタ)アクリレート、ニトロ安息香酸マグネシウム(メタ)アクリレート、ニトロ安息香酸亜鉛(メタ)アクリレート、ニトロ安息香酸銅(メタ)アクリレート、ニトロナフタレンカルボン酸マグネシウム(メタ)アクリレート、ニトロナフタレンカルボン酸亜鉛(メタ)アクリレート、ニトロナフタレンカルボン酸銅(メタ)アクリレート、プルビン酸マグネシウム(メタ)アクリレート、プルビン酸亜鉛(メタ)アクリレート、プルビン酸銅(メタ)アクリレート等の芳香族カルボン酸(メタ)アクリル酸金属エステルモノマー;
ジ(メタ)アクリル酸マグネシウム、ジ(メタ)アクリル酸亜鉛、ジ(メタ)アクリル酸銅等のジ(メタ)アクリル酸金属エステルモノマー;
オレイン酸マグネシウム(メタ)アクリレート、オレイン酸亜鉛(メタ)アクリレート、オレイン酸銅(メタ)アクリレート、エライジン酸マグネシウム(メタ)アクリレート、エライジン酸亜鉛(メタ)アクリレート、エライジン酸銅(メタ)アクリレート、リノール酸マグネシウム(メタ)アクリレート、リノール酸亜鉛(メタ)アクリレート、リノール酸銅(メタ)アクリレート、リノレン酸マグネシウム(メタ)アクリレート、リノレン酸亜鉛(メタ)アクリレート、リノレン酸銅(メタ)アクリレート、ステアロール酸マグネシウム(メタ)アクリレート、ステアロール酸亜鉛(メタ)アクリレート、ステアロール酸銅(メタ)アクリレート、リシノール酸マグネシウム(メタ)アクリレート、リシノール酸亜鉛(メタ)アクリレート、リシノール酸銅(メタ)アクリレート、リシノエライジン酸マグネシウム(メタ)アクリレート、リシノエライジン酸亜鉛(メタ)アクリレート、リシノエライジン酸銅(メタ)アクリレート、ブラシジン酸マグネシウム(メタ)アクリレート、ブラシジン酸亜鉛(メタ)アクリレート、ブラシジン酸銅(メタ)アクリレート、エルカ酸マグネシウム(メタ)アクリレート、エルカ酸亜鉛(メタ)アクリレート、エルカ酸銅(メタ)アクリレート、α-ナフトエ酸マグネシウム(メタ)アクリレート、α-ナフトエ酸亜鉛(メタ)アクリレート、α-ナフトエ酸銅(メタ)アクリレート、β-ナフトエ酸マグネシウム(メタ)アクリレート、β-ナフトエ酸亜鉛(メタ)アクリレート、β-ナフトエ酸銅(メタ)アクリレート等の不飽和カルボン酸(メタ)アクリル酸金属エステルモノマー;
が挙げられる。金属含有アクリルモノマー(Mc)は、2種以上を組み合わせて用いることもできる。
ジオレイン酸マグネシウム、ジオレイン酸亜鉛、ジオレイン酸銅、ジエライジン酸マグネシウム、ジエライジン酸亜鉛、ジエライジン酸銅、ジリノール酸マグネシウム、ジリノール酸亜鉛、ジリノール酸銅、ジリノレン酸マグネシウム、ジリノレン酸亜鉛、ジリノレン酸銅、ジステアロール酸マグネシウム、ジステアロール酸亜鉛、ジステアロール酸銅、ジリシノール酸マグネシウム、ジリシノール酸亜鉛、ジリシノール酸銅、ジリシノエライジン酸マグネシウム、ジリシノエライジン酸亜鉛、ジリシノエライジン酸銅、ジブラシジン酸マグネシウム、ジブラシジン酸亜鉛、ジブラシジン酸銅、ジエルカ酸マグネシウム、ジエルカ酸亜鉛、ジエルカ酸銅、ジα-ナフトエ酸マグネシウム、ジα-ナフトエ酸亜鉛、ジα-ナフトエ酸銅、ジβ-ナフトエ酸マグネシウム、ジβ-ナフトエ酸亜鉛、ジβ-ナフトエ酸銅等のジ不飽和カルボン酸金属エステルモノマー;
が挙げられる。金属含有非アクリルモノマー(Md)は、2種以上を組み合わせて用いることもできる。
ラジカル重合性モノマー(M)としては、前述した(メタ)アクリル系モノマー(Ma)や、非アクリル系モノマー(Mb)が使用できる。
有機過酸化物(O)は、-O-O-結合を有する有機化合物であって、分解により遊離ラジカルを生成するものである。この遊離ラジカルにより、ラジカル重合性モノマー(M)がラジカル重合する。
ジイソプロピルベンゼンヒドロパーオキシド、1,1,3,3-テトラメチルブチルヒドロパーオキシド、クメンヒドロパーオキシド、t-ブチルヒドロパーオキシド等のヒドロパーオキシド;
ジ(2-t-ブチルパーオキシイソプロピル)ベンゼン、ジクミルパーオキシド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン、t-ブチルクミルパーオキシド、ジ-t-ヘキシルパーオキシド、ジ-t-ブチルパーオキシド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン-3等のジアルキルパーオキシド;
ジイソブチリルパーオキシド、ジ(3,5,5-トリメチルヘキサノニル)パーオキシド、ジラウロイルパーオキシド、ジスクシニックアシッドパーオキシド、ジベンゾイルパーオキシド、ジ(3-メチルベンゾイル)パーオキシド、ベンゾイル(3-メチルベンゾイル)パーオキシド、ジ(4-メチルベンゾイル)パーオキシド等のジアシルパーオキシド;
メチルエチルケトンパーオキシド、シクロヘキサンパーオキシド、アセチルアセトンパーオキシド等のケトンパーオキサイド;
が挙げられる。有機過酸化物(O)は、2種以上を組み合わせて用いることもできる。
防汚塗料組成物には、有機過酸化物(O)の分解を促進するために分解促進剤(A)を配合することが好ましい。この分解促進剤(A)の作用により、常温(例えば20℃)で有機過酸化物(O)が分解し、ラジカル重合性モノマー(M)がラジカル重合するのを促進することができる。
N,N-ジメチル-p-トルイジン、N,N-ジエチル-p-トルイジン、N,N-ジエチルアニリン、N-(2-ヒドロキシエチル)-N-メチル-p-トルイジン、N,N-ビス(2-ヒドロキシエチル)-p-トルイジンまたはそのエチレンオキサイドもしくはプロピレンオキサイド付加物、N,N-ビス(2-ヒドロキシプロピル)-p-トルイジンまたはそのエチレンオキサイドもしくはプロピレンオキサイド付加物等のN,N-置換-p-トルイジン;4-(N,N-ジメチルアミノ)ベンズアルデヒド、4-[N,N-ビス(2-ヒドロキシエチル)アミノ]ベンズアルデヒド、4-(N-メチル-N-ヒドロキシエチルアミノ)ベンズアルデヒド等の4-(N,N-置換アミノ)ベンズアルデヒド;N,N-ジメチルアニリン、N,N-ビス(ヒドロキシエチル)アニリン、ジエタノールアニリン等のN,N-置換アニリン等の芳香族3級アミン;
アニリン、p-トルイジン、N-エチル-m-トルイジン、トリエタノールアミン、m-トルイジン、ジエチレントリアミン、ピリジン、フェニルモルホリン、ピペリジン等のその他のアミン;
メチルチオ尿素、ジエチルチオ尿素、アセチルチオ尿素、テトラメチルチオ尿素、エチレンチオ尿素等のチオ尿素化合物;
ナフテン酸コバルト、ナフテン酸銅、ナフテン酸マンガン、ナフテン酸ニッケル、バナジルアセチルアセトナート、チタンアセチルアセトナート等の金属塩;
が挙げられる。分解促進剤(A)は、2種以上を組み合わせて用いることもできる。
また、本発明の防汚塗料組成物の貯蔵安定性を向上させる目的で、ヒドロキノン、ヒドロキノンモノメチルエーテル、2,4-ジメチル-t-ブチルフェノールのような重合抑制剤を添加することができる。
本発明の防汚塗膜は、アクリルポリマー(P)、ラジカル重合性モノマー(M)、および有機過酸化物(O)を含有する防汚塗料組成物を基材に塗布した状態で、有機過酸化物(O)を分解させて得ることができる。このとき、アクリルポリマー(P)およびラジカル重合性モノマー(M)の少なくとも一方が、2価の金属エステル構造を有する。具体的には、前述の防汚塗料組成物を含む防汚塗料を被塗工物となる基材に塗工し、有機過酸化物(O)の分解温度以上で得られた塗工膜を乾燥させると共に、有機過酸化物(O)の分解によってラジカル重合性モノマー(M)を重合させることで、防汚塗膜を得ることができる。有機過酸化物(O)の分解温度が室温より低い場合は室温で乾燥できる。分解促進剤(A)を加えた場合は、有機過酸化物(O)の分解が起こる温度であれば、分解温度以下で乾燥できる。防汚塗料組成物は、塗工直前に混合することが好ましい。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM(プロピレングリコールメチルエーテル)66.3部および酸化亜鉛41部を仕込み、撹拌しながら75℃に昇温した。続いて、メタクリル酸43部、アクリル酸36部および水5部からなる混合物を、滴下ロートから3時間かけて滴下した。さらに2時間撹拌した後PGMを10部添加して、金属含有アクリルモノマー(Mc1)の溶液を得た。モノマー純分は54.8%であった。ここでモノマー純分とは、前記溶液中に含まれる金属含有アクリルモノマー(Mc1)の質量割合を意味する。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM58.7部および酸化亜鉛41部を仕込み、撹拌しながら75℃に昇温した。続いて、メタクリル酸39部、アクリル酸32部、オレイン酸28部、キシレン24.6部からなる混合物を、滴下ロートから3時間かけて滴下した。さらに2時間撹拌した後PGMを15部添加して、金属含有アクリルモノマー(Mc2)の溶液を得た。モノマー純分は54.9%であった。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM50部、キシレン100部、オレイン酸283部および酸化亜鉛41部を仕込み、撹拌しながら85℃に昇温し、85℃で3時間攪拌した。さらに2時間撹拌した後PGMを50部添加して、金属含有非アクリルモノマー(Md1)の溶液を得た。モノマー純分は60.2%であった。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM10部、キシレン47.1部およびエチルアクリレート4部を仕込み、撹拌しながら100℃に昇温した。続いて、メチルメタクリレート10部、エチルアクリレート62.6部、2-メトキシエチルアクリレート5.4部、製造例1で得られた金属含有モノマー(Ma1)の溶液32.7部(モノマー純分18部)、連鎖移動剤(日本油脂社製、商品名:ノフマーMSD)1部、AIBN(2,2’-アゾビス(イソブチロニトリル))2.5部およびAMBN(2,2’-アゾビス(2-メチルブチロニトリル))5.5部からなる混合物を、滴下ロートから6時間かけて滴下した。滴下終了後、さらにt-ブチルパーオクトエート0.5部およびキシレン5部の混合物を30分で滴下し、さらに1時間30分撹拌した後キシレンを5部添加して、固形分が56.0%、ガードナー粘度がZ6、酸価が84.5mgKOH/g、重量平均分子量が4,300の金属含有アクリルポリマー(Pm1)の溶液を得た。
金属含有モノマー(Ma1)の溶液に替えて金属含有モノマー(Ma2)の溶液を用いた以外は製造例4と同様にして、固形分が56.0%、ガードナー粘度が+Z4、酸価が77.2mgKOH/g、重量平均分子量が5,300の金属含有アクリルポリマー(Pm2)の溶液を得た。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM10部、キシレン47.1部およびエチルアクリレート4部を仕込み、撹拌しながら100℃に昇温した。続いて、メチルメタクリレート11.4部、エチルアクリレート72.0部、2-メトキシエチルアクリレート6.2部、製造例1で得られた金属含有モノマー(Ma1)の溶液11.6部(モノマー純分6.4部)、キシレン9.5部、連鎖移動剤(日本油脂社製、商品名:ノフマーMSD)1部、AIBN(2,2’-アゾビス(イソブチロニトリル))2.5部およびAMBN(2,2’-アゾビス(2-メチルブチロニトリル))2部からなる混合物を、滴下ロートから6時間かけて等速滴下した。滴下終了後、さらにt-ブチルパーオクトエート0.5部およびキシレン5部の混合物を30分で滴下し、さらに1時間30分撹拌した後キシレンを5部添加して、固形分が55.5%、ガードナー粘度がZ3、酸価が30.2mgKOH/g、重量平均分子量が9,000の金属含有アクリルポリマー(Pm3)の溶液を得た。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM10部、キシレン48.8部を仕込み、撹拌しながら100℃に昇温した。続いて、メチルメタクリレート10.6部、エチルアクリレート70.3部、2-メトキシエチルアクリレート5.7部、メタクリル酸7.3部、アクリル酸6.1部、キシレン13部、AIBN2.5部、AMBN4部からなる混合物を、滴下ロートから6時間かけて滴下した。滴下終了後、さらにt-ブチルパーオクトエート0.5部およびキシレン5部の混合物を30分で滴下し、さらに1時間30分撹拌した後キシレンを5部添加して、固形分が55.4%、ガードナー粘度酸価がN、酸価が94.8mgKOH/g、重量平均分子量が6,500の金属非含有アクリルポリマー(Pn1)の溶液を得た。
表2に示す配合割合で、ラジカル重合性モノマー(M)とアクリルポリマー(P)を混合した。その後、表2に示す配合割合で、20℃において分解促進剤を添加し、続いて有機過酸化物(O)を添加して、塗料の理論固形分が50~60%となるように防汚塗料組成物を調製した。ここで理論固形分とは、防汚塗料組成物中に含まれるラジカル重合性モノマー(M)とアクリルポリマー(P)の質量割合を意味する。そして、得られた防汚塗料組成物を速やかに所定の基板上に塗布し、室温で48時間乾燥して、乾燥膜厚が約180μmの塗膜を得た。防汚塗料組成物および塗膜に関し、以下の測定および評価を行った。
防汚塗料組成物の粘度を、B型粘度計によりNo.2~4のローターを用いて測定した。結果を表2に示した。
防汚塗料組成物を50g測りとり、室温にて攪拌し防汚塗料組成物の流動性がなくなるまでの時間を測定した。結果を表2に示した。
ガラス板上に塗膜を形成し、その塗膜の透明性を目視にて観察して、以下の基準で判定した。結果を表2に示した。
○ :透明。
△ :やや濁りあり。
× :濁りあり。ただし、析出物はなし。
××:濁りあり。析出物もあり。
あらかじめ防錆塗料が塗布されているサンドブラスト鋼板上に塗膜を形成し、その塗膜の面に対してキシレンを浸したガーゼで荷重500gをかけてラビングした。そして、塗膜が溶解してサンドブラスト鋼板が露出するまでの往復回数をカウントした。結果を表2に示した。
あらかじめ防錆塗料が塗布されているサンドブラスト鋼板上に塗膜を形成し、得られた試験片を滅菌濾過海水中に浸漬した後、20℃で1週間乾燥した。そして、塗膜に対し2mm間隔で基材まで達するクロスカットを入れ、2mm2の碁盤目を25個作り、その上にセロハンテープを貼り付けた後に急激に剥がした際の碁盤目の状態を観察して、以下の基準で判定した。結果を表2に示した。
◎:碁盤目の剥離および碁盤目の角の剥がれが全く観察されない。
○:碁盤目の剥離はないが、碁盤目の角の剥がれがみられる。
△:1~12個の碁盤目が剥離する。
×:13~25個の碁盤目が剥離する。
50mm×50mm×2mm(厚さ)の硬質塩化ビニル板上に塗膜を形成し、得られた試験片を海水中に設置した回転ドラムに取り付けた。そして、周速7.7m/s(15ノット)で回転させて、1ヵ月後および3ヵ月後の消耗膜厚を測定した。結果を表2に示した。
あらかじめ防錆塗料が塗布されているサンドブラスト鋼板上に塗膜を形成し、得られた試験片を人工海水中に1ヶ月間および3ヶ月間浸漬した後、20℃で1週間乾燥した。そして、塗膜表面を観察し、以下の基準で判定した。結果を表2に示した。
◎:クラックおよび剥離が全く観察されない。
○:クラックがわずかに観察される。
△:クラックおよび剥離が一部に観察される。
×:クラックおよび剥離が全面に観察される。
Claims (7)
- アクリルポリマー(P)、ラジカル重合性モノマー(M)、および有機過酸化物(O)を含有する防汚塗料組成物であって、前記アクリルポリマー(P)および前記ラジカル重合性モノマー(M)の少なくとも一方が、2価の金属エステル構造を有する防汚塗料組成物。
- 前記アクリルポリマー(P)の酸価が25mgKOH/g以上である請求項1に記載の防汚塗料組成物。
- 前記アクリルポリマー(P)が、2価の金属エステル構造を有するラジカル重合性モノマーを重合させて得られたものである請求項1または2に記載の防汚塗料組成物。
- さらに前記有機過酸化物(O)の分解促進剤(A)を含有する請求項1または2に記載の防汚塗料組成物。
- さらに前記有機過酸化物(O)の分解促進剤(A)を含有する請求項3に記載の防汚塗料組成物。
- アクリルポリマー(P)、ラジカル重合性モノマー(M)、および有機過酸化物(O)を含有する防汚塗料組成物を基材に塗布した状態で、前記有機過酸化物(O)を分解させる工程を有し、前記アクリルポリマー(P)および前記ラジカル重合性モノマー(M)の少なくとも一方が、2価の金属エステル構造を有する防汚塗膜の製造方法。
- 請求項6の製造方法により得られた防汚塗膜。
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KR20030025916A (ko) * | 2000-04-24 | 2003-03-29 | 니혼유시비에이에스에프코팅즈 가부시키가이샤 | 방오도료, 방오도막, 침수 구조체 및 방오방법 |
EP1167398B1 (en) * | 2000-06-28 | 2005-11-09 | Mitsubishi Rayon Co., Ltd. | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
TWI303654B (en) * | 2003-03-14 | 2008-12-01 | Mitsubishi Rayon Co | Antifouling coating composition |
-
2010
- 2010-04-06 EP EP10849423.8A patent/EP2557131B1/en active Active
- 2010-04-06 US US13/639,639 patent/US20130058889A1/en not_active Abandoned
- 2010-04-06 WO PCT/JP2010/056251 patent/WO2011125179A1/ja active Application Filing
- 2010-04-06 CN CN2010800659038A patent/CN102892844A/zh active Pending
- 2010-04-06 JP JP2010514738A patent/JP5732851B2/ja not_active Expired - Fee Related
- 2010-04-06 CN CN201710912229.6A patent/CN107513300A/zh active Pending
- 2010-04-06 KR KR1020127028951A patent/KR101750586B1/ko active IP Right Grant
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018184610A (ja) * | 2015-09-25 | 2018-11-22 | 三菱ケミカル株式会社 | 重合体溶液、重合体含有組成物、防汚塗料組成物及び重合体溶液の製造方法 |
WO2018008166A1 (ja) * | 2016-07-05 | 2018-01-11 | 三菱ケミカル株式会社 | 重合体含有組成物および防汚塗料組成物 |
US10954394B2 (en) | 2016-07-05 | 2021-03-23 | Mitsubishi Chemical Corporation | Polymer-containing composition and antifouling coating composition |
US11732144B2 (en) | 2016-07-05 | 2023-08-22 | Mitsubishi Chemical Corporation | Polymer-containing composition and antifouling coating composition |
Also Published As
Publication number | Publication date |
---|---|
JP5732851B2 (ja) | 2015-06-10 |
EP2557131B1 (en) | 2019-05-29 |
KR20130045264A (ko) | 2013-05-03 |
JPWO2011125179A1 (ja) | 2013-07-08 |
CN107513300A (zh) | 2017-12-26 |
US20130058889A1 (en) | 2013-03-07 |
KR101750586B1 (ko) | 2017-06-23 |
EP2557131A4 (en) | 2013-09-18 |
CN102892844A (zh) | 2013-01-23 |
EP2557131A1 (en) | 2013-02-13 |
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