WO2010038692A1 - 塗料組成物およびその製造方法、塗膜、ならびに水中構造物 - Google Patents
塗料組成物およびその製造方法、塗膜、ならびに水中構造物 Download PDFInfo
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- WO2010038692A1 WO2010038692A1 PCT/JP2009/066747 JP2009066747W WO2010038692A1 WO 2010038692 A1 WO2010038692 A1 WO 2010038692A1 JP 2009066747 W JP2009066747 W JP 2009066747W WO 2010038692 A1 WO2010038692 A1 WO 2010038692A1
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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
- C09D5/1612—Non-macromolecular compounds
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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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- 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
- C09D133/24—Homopolymers or copolymers of amides or imides
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
Definitions
- the present invention relates to a coating composition having improved low friction performance and a method for producing the same. Moreover, this invention relates to the underwater structure provided with the coating film formed with the said coating composition, and the said coating film.
- Organisms such as barnacles, mussels and algae tend to adhere to ships, fishing nets and other underwater structures. Due to the attachment of such living organisms, there is a problem that efficient operation is hindered in a ship or the like and fuel is wasted. In addition, problems such as clogging in fishing nets and shortened service life occur. Conventionally, in order to prevent organisms from adhering to these underwater structures, an antifouling paint is applied to the surface of the underwater structures.
- a paint capable of reducing such frictional resistance a paint containing a binder resin in which a metal such as organic tin, copper or zinc is introduced in the form of a salt into the acrylic resin side chain (self-polishing paint or hydrolyzable paint) Is also known in the art (for example, Japanese Patent Laid-Open No. 62-57464 (Patent Document 1)).
- the coating film formed from such a conventional self-polishing paint (hydrolyzable paint) is gradually hydrolyzed by water such as seawater at the time of ship navigation.
- the frictional resistance reduction effect is shown by reducing.
- the low friction performance of the conventional self-polishing paint is not sufficient, and a coating composition exhibiting higher low friction resistance has been demanded.
- Patent Document 2 International Publication No. 05/116155 (Patent Document 2), Japanese Patent Application Laid-Open No. 2006-328244 (Patent Document 3) and Japanese Patent Application Laid-Open No. 2007-169628 (Patent Document 4) are intended to further reduce frictional resistance.
- the coating composition a coating composition containing specific organic polymer particles or composite particles having a particle size of 0.05 to 100 ⁇ m is disclosed. However, these coating compositions also have room for improvement in terms of low friction performance.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a coating composition capable of obtaining an excellent low friction performance as compared with the prior art and a method for producing the same. Another object of the present invention is to provide a coating film having excellent low friction performance formed using such a coating composition, and an underwater structure such as a ship having the coating film.
- the present inventors have found that organic polymer particles having a specific particle size range composed of an organic polymer having a hydroxyl group and a cationic group in the same molecule, and a specific base resin as a binder resin
- the present inventors have found that a coating film composed of a coating composition containing, exhibits extremely good low friction performance, and has completed the present invention. That is, the present invention is as follows.
- the present invention comprises an organic polymer particle (A) having an organic polymer having a hydroxyl group and a cationic group in the molecule and having a weight average particle diameter of 10 to 35 ⁇ m, and the following general formula (1): -COO-M-OCO-A (1)
- M is a divalent or higher metal, and A represents an organic acid residue of a monobasic acid.
- R 1 , R 2 and R 3 are the same or different and each represents an isopropyl group or an n-butyl group.
- the following general formula (3) which has at least one of the groups represented by the formula in the side chain or bridges between the main chains: -COO-M-OCO- (3) (In the formula, M represents the same meaning as described above.)
- a base resin (B) having a cross-linked structure represented by the formula (1), wherein the content of the organic polymer
- the cationic group possessed by the organic polymer is preferably an amino group or an amide group.
- Suitable examples of the organic polymer having an amino group or an amide group include chitin, chitosan, and derivatives thereof.
- the base resin (B) contained in the coating composition of the present invention preferably contains an acrylic resin having a group represented by the general formula (1) in the side chain.
- the base resin (B) has at least one of the above general formulas (1) and (2) in the side chain and has a crosslinked structure represented by the above general formula (3) that crosslinks between main chains. May be included.
- the present invention also includes an organic polymer particle (A) having an organic polymer having a hydroxyl group and a cationic group in the molecule and having a weight average particle diameter of 10 to 35 ⁇ m, and the following general formula (1): -COO-M-OCO-A (1)
- M is a divalent or higher metal, and A represents an organic acid residue of a monobasic acid.
- R 1 , R 2 and R 3 are the same or different and each represents an isopropyl group or an n-butyl group.
- the following general formula (3) which has at least one of the groups represented by the formula in the side chain or bridges between the main chains: -COO-M-OCO- (3) (In the formula, M represents the same meaning as described above.)
- the present invention provides a coating film formed from the coating composition and an underwater structure having the coating film.
- a suitable example of the underwater structure is a ship.
- the present invention it is possible to provide a coating composition capable of obtaining a very excellent low friction performance as compared with the prior art and a coating film formed from the coating composition.
- a coating composition of the present invention By using the coating composition of the present invention to form a coating film on the surface of an underwater structure such as a ship, navigation fuel consumption can be reduced.
- the coating composition of the present invention comprises organic polymer particles (A) having an organic polymer having a hydroxyl group and a cationic group in the molecule and having a weight average particle diameter of 10 to 35 ⁇ m, and the following general formula (1): -COO-M-OCO-A (1)
- M is a divalent or higher metal, and A represents an organic acid residue of a monobasic acid.
- R 1 , R 2 and R 3 are the same or different and each represents an isopropyl group or an n-butyl group.
- the following general formula (3) which has at least one of the groups represented by the formula in the side chain or bridges between the main chains: -COO-M-OCO- (3) (In the formula, M represents the same meaning as described above.)
- a base resin (B) having a cross-linked structure represented by According to such a coating composition of the present
- the organic polymer particle (A) used in the present invention is composed of an organic polymer having both a hydroxyl group and a cationic group in the molecule.
- the coating film formed by the coating composition containing organic polymer particles (A) composed of such an organic polymer has a hydroxyl group and a cationic group on its surface, and thus has high hydrophilicity. Thereby, the outstanding low friction performance is shown.
- the coating film formed by the coating composition of the present invention exhibits excellent low friction performance because of the hydrogel on the coating film surface due to the hydroxyl group disposed on the coating film surface and the water in which the coating film is immersed. It is considered that one of the reasons is that a layer made of the above material is formed, thereby reducing the substantial surface roughness of the coating film surface.
- the coating film formed by the coating composition of the present invention is obtained by dispersing organic polymer particles (A) in a self-polishing type base resin (B) described later, and the base resin (B) When the elution occurs, the organic polymer particles (A) exposed on the coating film surface are released into water.
- the coating film formed by the coating composition of the present invention exhibits excellent low friction performance over a long period of time.
- the organic polymer particles (A) have a hydroxyl group and a cationic group
- the base resin (B) Since the release of the organic polymer particles (A) into the water is delayed due to the interaction with the metal M contained in the surface, the surface roughness reduction effect of the hydrogel layer can be sustained for a long time. it is conceivable that.
- the coating composition of the present invention may be in any form of water, NAD, and solvent, but the organic polymer particles (A) are not dissolved but dispersed in the coating composition. It is necessary.
- chitin, chitosan or a derivative thereof in which the cationic group is an amino group or an amide group is used as the organic polymer having both a hydroxyl group and a cationic group in the molecule constituting the organic polymer particle (A). It is preferable to use it.
- chitin (chemical name: poly- ⁇ 1-4-N-acetylglucosamine) is a linear nitrogen-containing compound having a hydroxyl group and an acetamide group represented by the molecular formula (C 8 H 13 NO 5 ) n. It is a saccharide.
- Chitosan (chemical name: poly- ⁇ 1-4-glucosamine) is a deacetylated product of chitin, which is a polysaccharide having a hydroxyl group and an amino group (and may further have an acetamide group).
- chitin In general, there is no clear boundary line between “chitin” and “chitosan”. However, in the present invention, those having a deacetylation rate of less than 60% are referred to as “chitin” and the deacetylation rate is low. Those over 60% will be called “chitosan”. In the present invention, a mixture of chitin and chitosan can be used as the organic polymer having both a hydroxyl group and a cationic group in the molecule.
- Examples of the chitin or chitosan derivative include those obtained by modifying or crosslinking chitin or chitosan with polyoxyethylene, an aldehyde group-containing compound, an organic acid compound, or the like.
- synthetic resin particles can also be used as the organic polymer particles (A).
- Synthetic resin particles can be produced by suspension polymerization of a radically polymerizable monomer composition in the presence of a hydrophilic polymer.
- a method of performing suspension polymerization by adding a suspension (addition suspension) of a radical polymerizable monomer composition to an aqueous liquid of a hydrophilic polymer is preferably used.
- polymerization is carried out by adding a preliminarily emulsified or suspended radical polymerizable monomer composition to an aqueous liquid of a hydrophilic polymer under heating and stirring.
- synthetic resin particles having a weight average particle diameter of 10 to 35 ⁇ m can be obtained.
- the aqueous liquid of the hydrophilic polymer is obtained by dissolving or dispersing the hydrophilic polymer in water.
- the hydrophilic polymer is not particularly limited, and may be a naturally derived polymer or a synthetic polymer.
- the hydrophilic polymer preferably has an appropriate amount of hydrophilic functional group and, if necessary, has a crosslinked chain.
- the hydrophilic functional group include a hydroxyl group, an amino group, a carboxyl group, an amide group, and a polyoxyethylene group.
- the hydrophilicity may become too high and the solubility in water or the like may become too high. In such a case, the hydrophilicity can be adjusted by introducing a hydrophobic group or crosslinking.
- Examples of the naturally-occurring polymer include polysaccharides such as chitin, chitosan, gum arabic, alginic acid, carrageenan, agar, chitansan gum, gellan gum, cellulose, xylose, starch, pullulan, pectin, roast bean gum, dextran and curdlan; Examples thereof include proteins such as keratin, collagen, silk, and ⁇ -polyglutamic acid (hereinafter referred to as ⁇ -PGA); and nucleic acids.
- hydrolyzing for example, hydroalkylation
- polyethylene glycolation for example, hydrophobization (for example, alkylation) or three-dimensionalization by performing hydrolysis, crosslinking reaction, etc. on these naturally derived polymers as necessary.
- Semi-synthetic polymers may be used.
- the above naturally-derived polymer and semi-synthetic polymer preferably have a cationic group.
- a cationic group By having a cationic group, the elution rate into seawater can be controlled.
- the cationic group is not particularly limited, and examples thereof include an amino group, an amide group, and a pyridine group.
- the chitin and chitosan may be modified or crosslinked with polyoxyethylene, an aldehyde group-containing compound, an organic acid compound, or the like as necessary.
- the synthetic polymer is not particularly limited, and examples thereof include polyvinyl alcohol resins such as acrylic resins, polyester resins, amine resins, and modified polyvinyl alcohol resins.
- the synthetic polymer is preferably a hydrophilic resin having a hydrophilic group such as a hydroxyl group, an amino group, or a carboxyl group. By adjusting the hydrophilicity / hydrophobicity and the cross-linking ratio by a known method, a synthetic polymer having appropriate hydrophilicity can be obtained.
- hydrophilic polymers starch, arabianori, ⁇ -carrageenan, gelatin, cellulose, chitin, chitosan and modified products thereof, polyvinyl alcohol, polyallylamine, polyvinylamine, poly (meth) acrylamide, poly (meth) It is preferably at least one hydrophilic resin selected from acrylic acid and copolymers thereof. Particularly preferred are chitin, chitosan and polyvinyl alcohol.
- the aqueous liquid of the hydrophilic polymer may be an acidic liquid in which an acidic monomer such as acrylic acid is dissolved.
- an acidic monomer such as acrylic acid
- the suspension (addition suspension) of the radical polymerizable monomer composition is preferably composed of a hydrophilic polymer, a radical polymerizable monomer composition, a polymerization initiator, and water. .
- an added suspension having the above composition By using an added suspension having the above composition, a suitable composite state of a hydrophilic polymer and a polymer obtained by radical polymerization can be obtained, and resin particles having a target particle diameter can be obtained. be able to. In particular, it is preferable to add a hydrophilic polymer to the added suspension.
- hydrophilic polymer contained in the suspension of the radical polymerizable monomer composition examples include the above-described hydrophilic polymers. It is preferable that the hydrophilic polymer contained in the aqueous liquid of the hydrophilic polymer and the hydrophilic polymer contained in the suspension of the radical polymerizable monomer composition are the same type.
- radical polymerizable monomer composition a monomer composition containing a hydroxyl group-containing radical polymerizable monomer and a cationic group-containing radical polymerizable monomer can be suitably used.
- the hydroxyl group-containing radical polymerizable monomer is not particularly limited.
- the cationic group-containing radical polymerizable monomer is not particularly limited.
- the content of the hydroxyl group-containing radical polymerizable monomer and the cationic group-containing radical polymerizable monomer in the radical polymerizable monomer composition is not particularly limited. It can be appropriately adjusted according to the low friction performance.
- the radical polymerizable monomer composition may contain a radical polymerizable monomer other than the hydroxyl group-containing radical polymerizable monomer and the cationic group-containing radical polymerizable monomer.
- the weight average particle diameter of the organic polymer particles (A) used in the present invention is a lower limit of 10 ⁇ m and an upper limit of 35 ⁇ m.
- the organic polymer particles (A) having a weight average particle diameter of less than 10 ⁇ m or exceeding 35 ⁇ m and comprising an organic polymer having a hydroxyl group and a cationic group in the molecule are used, the organic polymer particles (A) Although it is possible to improve the low friction performance as compared with a coating composition not containing benzene, the use of organic polymer particles (A) having a weight average particle diameter of 10 to 35 ⁇ m is particularly significantly low. The friction performance can be improved.
- the reason why the low friction performance is remarkably improved by using the organic polymer particles (A) having a weight average particle diameter of 10 to 35 ⁇ m is as follows.
- the “weight average particle diameter” of the organic polymer particles (A) blended in the coating composition means a weight average particle diameter measured by a laser diffraction method, more specifically. Means a value measured using “Laser Diffraction Particle Size Distribution Analyzer SALD-2200” manufactured by Shimadzu Corporation. Ethanol is used as a dispersion medium for particle size measurement, and the measurement temperature is 25 ° C.
- the “weight average particle diameter” of the organic polymer particles (A) contained in the coating composition is measured using a scanning electron microscope (SEM).
- the content of the organic polymer particles (A) is in the range of the lower limit of 0.5% by weight and the upper limit of 5.0% by weight in the total solid content (hereinafter referred to as paint solids) in the coating composition. . Even when the organic polymer particles (A) are used in a content of less than 0.5% by weight or more than 5.0% by weight, they are compared with a coating composition not containing the organic polymer particles (A). Although it is possible to sufficiently improve the low friction performance, it is possible to obtain excellent low friction performance over a longer period by setting the content to 0.5 to 5.0% by weight in the solid content of the paint. Can do.
- the content of the organic polymer particles (A) is set to 5.0% by weight or less in the solid content of the paint, the physical properties of the resulting coating film (for example, adhesion to the ground), and the present invention
- An antifouling agent (C) is contained in the paint composition, and a coating film is formed without adversely affecting the release property of the antifouling agent (C) into water when used as an antifouling paint composition.
- the total solid content (paint solid content) in a coating composition means the residue obtained by drying a coating composition at 105 degreeC for 1 hour.
- the reason why excellent low friction performance can be obtained over a long period of time by setting the content of the organic polymer particles (A) to 0.5 to 5.0% by weight in the solid content of the paint is as follows. A point can be mentioned.
- the coating composition of the present invention contains a base resin (B) as a binder resin.
- the base resin (B) contained in the coating composition of the present invention has the following general formula (1): -COO-M-OCO-A (1) (In the formula, M is a divalent or higher metal, and A represents an organic acid residue of a monobasic acid.) Or a group represented by the following general formula (2): —COO—Si (R 1 R 2 R 3 ) (2) (In the formula, R 1 , R 2 and R 3 are the same or different and each represents an isopropyl group or an n-butyl group.)
- the following general formula (3) which has at least one of the groups represented by the formula in the side chain or bridges between the main chains: -COO-M-OCO- (3) (In the formula, M represents the same meaning as described above.)
- the base resin (B) having a side chain and / or a crosslinked structure as described above is called a self-polishing polymer, and is used in water when used as a binder component for forming a coating film in a coating composition. It has a function of preventing adhesion of aquatic organisms such as barnacles by dissolving the resin gradually upon being decomposed. Further, by such a self-polishing function, when the base resin (B) is dissolved in water for a certain amount or more, the organic polymer particles (A) exposed on the surface of the coating film are released into the water, and a new organic polymer Since the molecular particles (A) are exposed on the surface, high low friction performance by the organic polymer particles (A) can be maintained.
- the coating composition of the present invention can be suitably used as an antifouling coating composition exhibiting excellent low friction performance.
- Examples of the base resin (B) used in the present invention include the following.
- (III) an acrylic resin having a group represented by the general formula (2) in the side chain hereinafter referred to as acrylic resin (III)
- (IV) An acrylic resin having a crosslinked structure represented by the above general formula (3) for crosslinking between polymer main chains hereinafter referred to as acrylic resin (IV)).
- the acrylic resin (I) is an acrylic resin having at least one group represented by the general formula (1) in the acrylic resin side chain.
- the acrylic resin (I) can be produced, for example, by the following method (a) or (b).
- (A) A resin obtained by copolymerizing a polymerizable unsaturated organic acid and another copolymerizable unsaturated monomer is reacted with a metal compound and a monobasic acid, or a monobasic acid A method of transesterification using a metal ester,
- B A method of copolymerizing a metal-containing polymerizable unsaturated monomer and another copolymerizable unsaturated monomer.
- a resin obtained by copolymerizing a polymerizable unsaturated organic acid and another copolymerizable unsaturated monomer is reacted with a metal compound and a monobasic acid, or Transesterification using a metal ester of a monobasic acid can be carried out by a conventionally known method, but it is desirable to carry out heating, stirring, etc. below the decomposition temperature of the metal ester.
- the polymerizable unsaturated organic acid used in the above method (a) is not particularly limited, and examples thereof include those having one or more carboxyl groups, such as (meth) acrylic acid and the like.
- Examples include diphthalic acid adducts of unsaturated monobasic hydroxyalkyl esters such as phthalic acid adducts of 2-hydroxyethyl (meth) acrylate and succinic acid adducts of 2-hydroxyethyl (meth) acrylate.
- These polymerizable unsaturated organic acids may be used alone or in combination of two or more.
- the metal-containing polymerizable unsaturated monomer used in the method (b) is a polymerizable unsaturated monomer having a group represented by the general formula (1).
- the metal-containing polymerizable unsaturated monomer reacts with a metal compound and a monobasic acid in the same manner as in the method (a) using a polymerizable unsaturated organic acid as used in the method (a). Alternatively, it can be obtained by a method of transesterification using a metal ester of a monobasic acid.
- copolymerizable unsaturated monomers used in the above methods (a) and (b) are not particularly limited, and examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) I-propyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and ( (Meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the ester moiety such as stearyl acrylate; carbon in the ester moiety such as 2-hydroxypropyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate 1 to 20 hydroxyl group-containing (meth) acrylic acid alkyl esters; phenyl (meth) acrylate and (meth) acrylic acid
- (meth) acrylic acid esters include (meth) acrylamide; vinyl compounds such as styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyltoluene, acrylonitrile; crotonic acid Esters; diesters of unsaturated dibasic acids such as maleic acid diesters and itaconic acid diesters.
- the ester portion of the (meth) acrylic acid ester is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
- (meth) acrylic acid esters preferably used are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate.
- the said other copolymerizable unsaturated monomer may be used independently, and may use 2 or more types together.
- the metal compound is not particularly limited, and examples thereof include metal oxides, metal hydroxides, metal chlorides, metal sulfides, organic acid metal salts, and metal basic carbonates. These may be used alone or in combination of two or more.
- This metal compound serves as a supply source of the metal M included in the base resin (B).
- the metal contained in the metal compound (that is, the metal M included in the base resin (B)) is a metal having a valence of 2 or more, and preferably copper (II) and / or zinc (II).
- the monobasic acid is not particularly limited, and examples thereof include monobasic acids having 2 to 30 carbon atoms. Among them, monobasic cyclic organic acids are preferable.
- the monobasic acid constitutes a “—OCO-A” (A represents an organic acid residue of a monobasic acid) in the group represented by the general formula (1).
- the monobasic cyclic organic acid is not particularly limited, and examples thereof include those having a cycloalkyl group such as naphthenic acid, resin acids such as tricyclic resin acids, and salts thereof.
- the tricyclic resin acid is not particularly limited, and examples thereof include a monobasic acid having a diterpene hydrocarbon skeleton.
- monobasic acids having a diterpene-based hydrocarbon skeleton include compounds having an abietane, pimaran, isopimaran, and labdane skeletons, and more specifically, abietic acid, neoabietic acid, dehydroabietic acid, and hydrogenated abietic acid And parastrinic acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, and sandaracopimalic acid.
- the monobasic cyclic organic acid does not need to be highly purified, and for example, pine resin, pine resin acid, and the like can be used.
- examples of such include rosins, hydrogenated rosins, and disproportionated rosins.
- the rosins here are gum rosin, wood rosin, tall oil rosin and the like. Rosin, hydrogenated rosin and disproportionated rosin are preferable in that they are inexpensive and easily available, have excellent handling properties, and exhibit long-term durability and antifouling properties with low friction performance.
- monobasic cyclic organic acids may be used alone or in combination of two or more.
- monobasic acids that can be used in the present invention include, for example, acetic acid, (meth) acrylic acid, propionic acid, butyric acid, lauric acid, palmitic acid, 2-ethylhexanoic acid, Examples thereof include monobasic acids having about 1 to 30 carbon atoms such as stearic acid, linoleic acid, oleic acid, chloroacetic acid, fluoroacetic acid, valeric acid, versatic acid, 12-hydroxystearic acid and hydrogenated castor oil fatty acid. it can.
- it is a monobasic acid having 5 to 20 carbon atoms.
- Monobasic acids other than these monobasic cyclic organic acids may be used alone or in combination of two or more.
- the lower limit of 5 mol% and the upper limit of 100 mol% are monobasic cyclic organic among monobasic acids used.
- An acid is preferred. That is, among the organic acid residues of the monobasic acid in the general formula (1), it is preferable that the lower limit is 5 mol% and the upper limit is 100 mol% is a monobasic cyclic organic acid.
- the content of the monobasic cyclic organic acid is more preferably a lower limit of 15 mol% and an upper limit of 100 mol%, and further preferably a lower limit of 25 mol% and an upper limit of 100 mol%.
- the base resin (B) is moderately hydrolyzed, so that the long-lasting low-friction performance and long-term antifouling are achieved. It is possible to improve the crack resistance of the coating film.
- the acid value of the monobasic cyclic organic acid used for introducing the monobasic cyclic organic acid residue is preferably a lower limit of 70 mgKOH / g and an upper limit of 300 mgKOH / g, more preferably a lower limit of 120 mgKOH / g and an upper limit of 250 mgKOH / g. is there.
- the base resin (B) is moderately hydrolyzed, so that a coating film that is superior in long-term durability with low friction and long-term antifouling properties can be formed.
- the acid value of the monobasic cyclic organic acid is more preferably a lower limit of 120 mgKOH / g and an upper limit of 220 mgKOH / g.
- the number average molecular weight of the resin obtained by copolymerizing a polymerizable unsaturated organic acid and other copolymerizable unsaturated monomer is determined by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the lower limit is preferably in the range of 2000 and the upper limit is 100,000, and more preferably in the range of the lower limit 3000 and the upper limit 40000. If it is less than 2000, the film-forming property of the coating film may be lowered, and if it exceeds 100,000, the resulting coating composition will not be suitable for practical use because of poor storage stability, and a large amount of dilution solvent may be applied during coating. It is not preferable in terms of public health, economy, etc.
- the resin obtained by copolymerizing a polymerizable unsaturated organic acid and another copolymerizable unsaturated monomer preferably has an acid value of 70 to 300 mgKOH / g. . If it is less than 70 mgKOH / g, the amount of the metal salt to be bonded to the side chain tends to be small, and there is a tendency that an appropriate hydrolyzability of the base resin (B) cannot be obtained, and the acid value exceeds 300 mgKOH / g. And the elution rate of the coating film obtained is too fast, and there is a tendency that long-term durability and long-term antifouling properties with low friction performance are not sufficiently obtained.
- the acrylic resin (I) obtained as described above has at least one group represented by the general formula (1) in the side chain.
- the metal M is a divalent or higher metal, preferably copper (II) or zinc (II).
- the metal M is preferably contained in the acrylic resin (I) solid content within the range of 0.05% by weight lower limit and 20% by weight upper limit. If it is less than 0.05% by weight, even if the metal salt portion in the resulting coating film is hydrolyzed, the dissolution of the entire resin tends to be very slow, so that the antifouling performance of the coating film tends to decrease. On the other hand, if it exceeds 20% by weight, the dissolution rate of the resulting coating film is too high, and there is a tendency that long-term durability and long-term antifouling properties with low friction performance cannot be obtained sufficiently.
- the content of the metal M is more preferably a lower limit of 0.5% by weight and an upper limit of 15% by weight.
- the group represented by the general formula (1) is contained in the acrylic resin (I) solid content within the range of the lower limit of 0.001 mol / g and the upper limit of 0.006 mol / g. Is preferred.
- the dissolution rate of the acrylic resin (I) which is the base resin (B) into water becomes moderate, and the low friction performance is achieved.
- a coating film having long-lasting durability and long-term antifouling property is easily obtained.
- the acrylic resin (II) is an acrylic resin having at least one group represented by the general formula (1) and at least one group represented by the general formula (2) on the acrylic resin side chain.
- R 1 , R 2 and R 3 are the same or different and each represents an isopropyl group or an n-butyl group.
- R 1 , R 2 and R 3 are preferably all isopropyl groups.
- the acrylic resin (II) is preferably obtained from a monomer mixture containing a triorganosilyl (meth) acrylate represented by the following general formula (4). Thereby, it becomes easy to obtain a coating film exhibiting long-lasting low-friction performance and long-term antifouling properties.
- Z represents a hydrogen atom or a methyl group.
- R 4 , R 5 and R 6 are the same or different and each represents an isopropyl group or an n-butyl group, preferably all isopropyl groups.
- triorganosilyl (meth) acrylate represented by the general formula (4) include tri-i-propylsilyl (meth) acrylate and tri-n-butylsilyl (meth) acrylate.
- the triorganosilyl (meth) acrylate represented by the general formula (4) is preferably tri-i-propylsilyl (meth) acrylate because a stable polishing rate (polishing rate) can be maintained for a long period of time.
- the said triorganosilyl (meth) acrylate may be used independently and may use 2 or more types together.
- the acrylic resin (II) can be produced by the following method (c) or (d).
- (C) a first step of polymerizing a polymerizable unsaturated organic acid, a triorganosilyl (meth) acrylate represented by the general formula (4), and another copolymerizable unsaturated monomer; and , A method comprising a second step of reacting a resin obtained in the first step with a metal compound and a monobasic acid, or transesterifying using a metal ester of a monobasic acid,
- (D) A method of copolymerizing a metal-containing polymerizable unsaturated monomer, a triorganosilyl (meth) acrylate represented by the general formula (4), and another copolymerizable unsaturated monomer.
- the first step of the method (c) includes a polymerizable unsaturated organic acid (for example, 3 to 50% by weight), a triorganosilyl (meth) acrylate represented by the general formula (4) (for example, 90 to 5% by weight). ) And other copolymerizable unsaturated monomers.
- the method for polymerizing these monomer components is not particularly limited.
- a monomer mixture composed of a polymerizable unsaturated organic acid, triorganosilyl (meth) acrylate, and other copolymerizable unsaturated monomers is mixed with azo.
- a method of dropping in a solvent such as xylene or n-butanol and reacting under heating conditions can be exemplified.
- a solvent such as xylene or n-butanol
- the polymerizable unsaturated organic acid and other copolymerizable unsaturated monomers those described for the acrylic resin (I) can be used.
- the number average molecular weight of the resin obtained by the first step of the method (c) is preferably in the range of a lower limit of 2000 and an upper limit of 100,000 in terms of standard polystyrene using gel permeation chromatography (GPC). More preferably, the lower limit is within the range of 3000 and the upper limit is 40000. If it is less than 2000, the film-forming property of the coating film may be lowered, and if it exceeds 100,000, the resulting coating composition will not be suitable for practical use because of poor storage stability, and a large amount of dilution solvent may be applied during coating. Is not preferable in terms of public health and economy.
- the resin obtained by the first step of the method (c) preferably has an acid value of 30 to 300 mgKOH / g.
- the amount is less than 30 mgKOH / g, the amount of the metal salt to be bonded to the side chain tends to be small, and there is a tendency that an appropriate hydrolyzability of the base resin (B) cannot be obtained, and the acid value exceeds 300 mgKOH / g.
- the elution rate of the coating film obtained is too fast, and there is a tendency that long-term durability and long-term antifouling properties with low friction performance are not sufficiently obtained.
- the second step of the method (c) is a step of reacting the resin obtained in the first step with a metal compound and a monobasic acid, or transesterifying using a metal ester of a monobasic acid. is there. That is, by this second step, the group represented by the general formula (1) is formed on the resin side chain.
- the resin obtained by the first step is reacted with a metal compound and a monobasic acid, or a method of transesterifying using a metal ester of a monobasic acid, although it can be carried out by a conventionally known method, it is desirable to carry out heating, stirring, etc. below the decomposition temperature of the metal ester.
- metal-containing polymerizable unsaturated monomer used in the method (d) those described for the acrylic resin (I) can be used.
- the copolymerization in the method (d) can be carried out in the same manner as in the above method (c).
- the group represented by the general formula (1) is contained in the acrylic resin (II) solid content within the range of the lower limit of 0.001 mol / g and the upper limit of 0.006 mol / g. Is preferred.
- the group represented by the general formula (2) is preferably contained in the acrylic resin (II) solid content within a range of a lower limit of 0.0004 mol / g and an upper limit of 0.004 mol / g.
- the acrylic resin (III) is an acrylic resin having at least one group represented by the above general formula (2) on the acrylic resin side chain, and is self-polishing type like the acrylic resins (I) and (II). It is a polymer.
- acrylic resin (III) examples include those obtained by a method of reacting a polymerizable unsaturated monomer and a monomer having a triorganosilyl group.
- the general formula (4) It is preferable that it is a thing obtained by superposing
- the other copolymerizable unsaturated monomer is not particularly limited, and examples include those described in the acrylic resin (I) and polymerizable unsaturated organic acids described in the acrylic resin (I). it can. These polymerizable unsaturated organic acids and other copolymerizable unsaturated monomers may be used alone or in combination of two or more.
- Z represents a hydrogen atom or a methyl group.
- R 4 , R 5 and R 6 are the same or different and each represents an isopropyl group or an n-butyl group, preferably all isopropyl groups.
- triorganosilyl (meth) acrylate represented by the general formula (4) include tri-i-propylsilyl (meth) acrylate and tri-n-butylsilyl (meth) acrylate.
- the triorganosilyl (meth) acrylate represented by the general formula (4) is preferably tri-i-propylsilyl (meth) acrylate because a stable polishing rate (polishing rate) can be maintained for a long period of time.
- the said triorganosilyl (meth) acrylate may be used independently and may use 2 or more types together.
- the triorganosilyl (meth) acrylate represented by the general formula (4) is preferably contained in the monomer mixture used for polymerization in an amount of 90% by weight and 5% by weight in the lower limit. If it exceeds 90% by weight, peeling may occur in the coated film, and if it is less than 5% by weight, the proportion of triorganosilyl groups in the resulting resin decreases, and the long-lasting low friction performance and It tends to be difficult to obtain a coating film exhibiting long-term antifouling properties.
- the content of the triorganosilyl (meth) acrylate represented by the general formula (4) in the monomer mixture is more preferably in the range of 70 wt% for the upper limit and 10 wt% for the lower limit.
- the method for polymerizing the monomer mixture is not particularly limited.
- a monomer mixture composed of triorganosilyl (meth) acrylate and other copolymerizable unsaturated monomers is polymerized with an azo compound or a peroxide.
- Examples of the method include preparing a mixed solution by mixing with an initiator and then dropping the solution into a solvent such as xylene and n-butanol and reacting under heating conditions.
- the number average molecular weight of the acrylic resin (III) is preferably in the range of a lower limit of 2000 and an upper limit of 100,000 in terms of standard polystyrene using gel permeation chromatography (GPC), and a range of a lower limit of 3000 and an upper limit of 40000. More preferably, it is within. If it is less than 2000, the film-forming property of the coating film may be lowered, and if it exceeds 100,000, the resulting coating composition will not be suitable for practical use because of poor storage stability, and a large amount of dilution solvent may be applied during coating. It is not preferable in terms of public health, economy, etc.
- the group represented by the general formula (2) is contained in the acrylic resin (III) solid content within the range of the lower limit of 0.0004 mol / g and the upper limit of 0.004 mol / g. Is preferred.
- the dissolution rate of the acrylic resin (III) which is the base resin (B) into water becomes moderate, and low friction performance is achieved.
- a coating film having long-lasting durability and long-term antifouling property is easily obtained.
- the group represented by the general formula (2) is contained in the acrylic resin (III) solid content within a range of a lower limit of 10% by weight and an upper limit of 90% by weight. If the amount is less than 10% by weight, the self-polishing property may be insufficient. If the amount exceeds 90% by weight, the dissolution of the coating film may be too fast to hold the coating film for a long time.
- the content is more preferably in the range of a lower limit of 30% by weight and an upper limit of 80% by weight.
- the acrylic resin (IV) is an acrylic resin having at least one cross-linked structure represented by the general formula (3) that cross-links between polymer main chains.
- M represents a divalent or higher metal, preferably a divalent metal such as Mg, Zn, or Ca.
- Examples of a method for producing an acrylic resin having a crosslinked structure containing a divalent metal include a method of reacting (adding) a divalent metal compound to a carboxyl group-containing acrylic resin, and a polymerizable monomer containing a divalent metal. Examples thereof include a method of polymerizing a monomer composition containing a polymer by solution polymerization or the like. The method for solution polymerization is not particularly limited, and a known method can be used.
- the acrylic resin (IV) may have a group represented by the general formula (1) and / or the general formula (2) in the side chain.
- the monomers described in the acrylic resins (I) to (III) are used as monomers for preparing the acrylic resin (IV). Can be used as part of the component.
- the amount of the metal of the acrylic resin (IV) is 0.05 to 20% by weight in the total amount of the metal in the crosslinked structure and the metal in the group represented by the general formula (1) in the resin solid content. Is preferred.
- the acrylic resins (I) to (IV) may be used alone as the base resin (B), or any two or more of them may be used in combination.
- the coating composition of the present invention may contain other binder resin together with the base resin (B) in order to adjust the physical properties of the coating film and the consumption rate of the coating film.
- the other binder resin is not particularly limited, and examples thereof include chlorinated rubber, polyvinyl acetate, alkyd resin, polyester resin, and polyvinyl chloride.
- acrylic resins other than the acrylic resins (I) to (IV) may be used. Examples of acrylic resins other than the acrylic resins (I) to (IV) include poly (meth) acrylic acid alkyl esters.
- the coating composition of the present invention contains, if necessary, silicon oil; wax; petrolatum; liquid paraffin; rosin; hydrogenated rosin; naphthenic acid; fatty acid; rosin, hydrogenated rosin, naphthenic acid and fatty acid divalent metal. It may contain additives such as salt; chlorinated paraffin; polyvinyl alkyl ether; polypropylene sebacate; partially hydrogenated terphenyl; and polyether polyol. Other binder resins and additives may be used alone or in combination of two or more.
- the weight ratio of the solid content of the base resin (B) to the solid content of the other binder resin [base resin (B) ]: [Other resin binder] is preferably 100: 0 to 50:50.
- the coating composition of the present invention may be in any form such as solvent-based coating, NAD, water-based coating.
- a resin solution obtained by reacting in an organic solvent can be used as it is.
- the base resin (B) (and other binder resin added if necessary) for example, the base resin (B) obtained by the above method (and if necessary)
- a solution obtained by dispersing an organic solvent solution of other binder resin) added in water by a known method can be used.
- the dispersion method is not particularly limited, and is a method of emulsifying with an emulsifier; a part of the carboxyl group of the base resin (B) (and other binder resin added if necessary) using a basic compound. Examples thereof include a method of dispersing by summing. Moreover, when setting it as an aqueous coating material, you may use what is obtained by emulsion polymerization as a metal containing acrylic resin (acrylic resin (IV) etc.) which has the said crosslinked structure.
- the basic compound is not particularly limited, and examples thereof include alkylamines such as ammonia (aqueous solution), triethylamine, trimethylamine, and butylamine; ethanolamine, 2-dimethylaminoethanol, triethanolamine, diethylethanolamine, dimethylethanol.
- alkylamines such as ammonia (aqueous solution), triethylamine, trimethylamine, and butylamine
- ethanolamine 2-dimethylaminoethanol, triethanolamine, diethylethanolamine, dimethylethanol.
- examples include amines and alcohol amines such as aminomethylpropanol; morpholine and the like. Of these, ammonia (aqueous solution) and ethanolamine are preferable. Only 1 type may be used for a basic compound and it may use 2 or more types together.
- additives such as an antifouling agent, a plasticizer, a pigment, and a solvent can be added to the coating composition of the present invention.
- 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.
- antifouling agent examples include, for example, zinc oxide, cuprous oxide, manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s.
- the content of the antifouling agent is preferably in the range of a lower limit of 0.1% by weight and an upper limit of 80% by weight in the solid content of the paint. If it is less than 0.1% by weight, the antifouling effect by the antifouling agent cannot be expected, and if it exceeds 80% by weight, defects such as cracks and peeling may occur in the coating film.
- the content of the antifouling agent is more preferably in the range of a lower limit of 1% by weight and an upper limit of 60% by weight.
- 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 dibenzoate and pentaerythritol Glycol ester plasticizers such as alkyl esters; Phosphate ester plasticizers such as triclendrin phosphate and trichloroethyl phosphate; Epoxy plasticizers such as epoxy soybean oil and epoxy octyl stearate; Dioctyl tin laurate and dibutyl tin laurate Organic tin-based plasticizers; trioctyl trimellitic acid, triacetylene, and the like. These plasticizers may be used alone or in combination of two or more.
- the pigment examples include extender pigments such as precipitated barium, talc, clay, chalk, silica white, alumina white and bentonite; titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, graphite, bengara, Examples thereof include coloring pigments such as chrome yellow, phthalocyanine green, phthalocyanine blue, and quinacridone. These pigments 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
- coloring pigments such as chrome yellow, phthalocyanine green, phthalocyanine blue, and quinacridone. These pigments may be used alone or in combination of two or more.
- the solvent examples include hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane and white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethers such as ethylene glycol dibutyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethyl isobutyl ketone and methyl isobutyl Ketones such as ketones; n-butanol And the like, and alcohols such as propyl alcohol.
- hydrocarbons such as
- Additives other than the above include, for example, monobasic organic acids such as monobutyl phthalate and monooctyl succinate, camphor, castor oil, etc .; water binder, sagging agent; color separation inhibitor; anti-settling agent; antifoaming agent Etc.
- the coating composition of the present invention includes, for example, the organic polymer particles (A) and further the above-mentioned base resin (B) and other binder resin added as necessary, or a resin composition containing these.
- Add additives such as antifouling agents, plasticizers, coating film consumption regulators, pigments, solvents, etc. according to the conditions, and mix by using a blender such as a ball mill, pebble mill, roll mill, sand grind mill, etc. be able to.
- the coating composition of the present invention is superior to conventional coating compositions in that good low friction performance can be imparted even when applied to a ship traveling at a speed of about 10 to 30 knots. Is.
- the coating composition of the present invention can significantly contribute to the reduction of navigation fuel consumption, particularly as a ship bottom coating.
- the coating film of the present invention is formed from the above-described coating composition of the present invention. Specifically, after the coating composition of the present invention is applied to the surface of an article to be coated according to a conventional method, It can be formed by stripping off the solvent under heating.
- the method for applying the coating composition is not particularly limited, and examples thereof include conventionally known methods such as dipping, spraying, brush coating, roller, electrostatic coating, and electrodeposition coating. Although it does not restrict
- the coating film of the present invention is formed by the coating composition of the present invention, it has excellent low friction performance. Moreover, the coating film of this invention can maintain the outstanding low friction performance over a long period of time. Furthermore, the coating film of this invention is excellent also in antifouling property and crack resistance.
- This resin solution D contains an acrylic resin having a crosslinked structure containing Zn as a base resin.
- xylene was added to a four-necked flask equipped with a cooling tube, a thermometer, a stirrer, and a nitrogen introducing tube, and heated to 100 ° C.
- 30 g of methyl methacrylate, 55 g of tri-i-propylsilyl methacrylate, 5 g of 2-methoxyethyl methacrylate, 20 g of the above monomer solution and 1.5 g of t-butylperoxy 2-ethylhexanoate The solution was added dropwise over 3 hours and then kept warm for 3 hours to obtain a resin solution E having a solid content concentration of 50.5% by weight.
- This resin solution E contains, as a base resin, an acrylic resin having a group represented by the general formula (1) and a group represented by the general formula (2) in the side chain.
- This resin solution F contains an acrylic resin having a crosslinked structure containing Zn as a base resin.
- This resin solution G contains, as a base resin, an acrylic resin having a group represented by the general formula (1) and a group represented by the general formula (2) in the side chain.
- chitosan manufactured by Dainippon Seika Kogyo Co., Ltd.
- organic high polymer organic polymer particles composed of chitosan having weight average particle sizes of 5, 15, 30, and 60 ⁇ m, respectively
- SALD-2200 organic polymer particles having weight average particle sizes of 5, 15, 30, and 60 ⁇ m, respectively
- each blending component was dispersed with glass beads using a disper to prepare a coating composition.
- the unit of numerical values of the blending amounts is “g”.
- the antifouling agents a to h used are as follows. The following evaluation was performed about the obtained coating composition.
- Antifouling agent a zinc dimethyldithiocarbamate antifouling agent b: N- (fluorodichloromethylthio) phthalimide antifouling agent c: 3-iodo-2-propenylbutyl carbamate antifouling agent d: pyridine-triphenylborane antifouling agent e : Rodin copper antifouling agent f: Cuprous oxide antifouling agent g: Zinc pyrithione antifouling agent h: Copper pyrithione (friction resistance test)
- the obtained coating composition is applied to a cylindrical cylinder made of polyvinyl chloride having a diameter of 10 cm and a height of 10 cm, dried to form a coating film, and then rotated in seawater (around 10 knots in terms of peripheral speed), and a torque meter
- the frictional resistance was measured by The frictional resistance of a smooth PVC cylindrical drum mirror-finished by buffing was measured as a standard.
- Friction resistance was evaluated immediately after immersion in seawater (initial stage) and after immersion for 1 month.
- the energy consumption basic unit in navigation of a ship meaning energy consumption per unit production value, so that the basic unit increases, the so-called fuel efficiency deteriorates
- the obtained coating composition was applied to a 10 cm ⁇ 30 cm acrylic plate so that the dry film thickness was about 200 ⁇ m, and dried at room temperature for two days and nights to obtain a test coating film plate. Thereafter, an immersion test was carried out for 12 months at a seaside laboratory at Nippon Paint Marine Co., Ltd., Tamano City, Okayama Prefecture. The adhesion of organisms to the test coating plate after the test was evaluated visually. The evaluation results are shown in Tables 1 and 2.
- A No attachment of large organisms such as barnacles, mussels and algae.
- B Large organisms such as barnacles, mussels and algae were attached.
- the obtained coating composition was applied to a 10 cm ⁇ 30 cm acrylic plate so that the dry film thickness was about 200 ⁇ m, and dried at room temperature for two days and nights to obtain a test coating film plate. Then, it was immersed for 1 week in a seaside laboratory of Nippon Paint Marine Co., Ltd., Tamano City, Okayama Prefecture, and dried for 3 days. After this immersion and drying were repeated five times, the presence or absence of cracks in the coating film was visually evaluated. The evaluation results are shown in Tables 1 and 2.
- Example 7 Comparing Example 7 in which the content of organic polymer particles in the solid content of the paint is 5.0% by weight and Comparative Example 6 in which the content of organic polymer particles is 6.7% by weight
- Example 7 in particular, the frictional resistance coefficient after one month is three times smaller, and the low friction performance after one month is remarkably improved with these contents as a boundary.
- each blending component was dispersed with glass beads using a disper to prepare a coating composition.
- the unit of the numerical value of the blending amount in Table 3 is “g”.
- the used antifouling agents d to h are as described above.
- the obtained coating compositions were evaluated in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 11. The evaluation results are shown in Table 3.
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Abstract
Description
-COO-M-OCO-A (1)
(式中、Mは、2価以上の金属であり、Aは、一塩基酸の有機酸残基を表す。)
で示される基、あるいは、下記一般式(2):
-COO-Si(R1R2R3) (2)
(式中、R1、R2およびR3は、同一または異なって、イソプロピル基またはn-ブチル基を表す。)
で示される基の少なくともいずれかを側鎖に有するか、または、主鎖間を架橋する下記一般式(3):
-COO-M-OCO- (3)
(式中、Mは、上記と同じ意味を表す。)
で示される架橋構造を有する基体樹脂(B)と、を含有し、有機高分子粒子(A)の含有量が、塗料固形分中、0.5~5.0重量%である塗料組成物を提供する。
-COO-M-OCO-A (1)
(式中、Mは、2価以上の金属であり、Aは、一塩基酸の有機酸残基を表す。)
で示される基、あるいは、下記一般式(2):
-COO-Si(R1R2R3) (2)
(式中、R1、R2およびR3は、同一または異なって、イソプロピル基またはn-ブチル基を表す。)
で示される基の少なくともいずれかを側鎖に有するか、または、主鎖間を架橋する下記一般式(3):
-COO-M-OCO- (3)
(式中、Mは、上記と同じ意味を表す。)
で示される架橋構造を有する基体樹脂(B)とを、有機高分子粒子(A)の含有量が、塗料固形分中、0.5~5.0重量%となるように混合する工程を備える塗料組成物の製造方法を提供する。
-COO-M-OCO-A (1)
(式中、Mは、2価以上の金属であり、Aは、一塩基酸の有機酸残基を表す。)
で示される基、あるいは、下記一般式(2):
-COO-Si(R1R2R3) (2)
(式中、R1、R2およびR3は、同一または異なって、イソプロピル基またはn-ブチル基を表す。)
で示される基の少なくともいずれかを側鎖に有するか、または、主鎖間を架橋する下記一般式(3):
-COO-M-OCO- (3)
(式中、Mは、上記と同じ意味を表す。)
で示される架橋構造を有する基体樹脂(B)と、を含有するものである。かかる本発明の塗料組成物によれば、優れた低摩擦性能を示す塗膜を形成することができる。以下、本発明の塗料組成物について詳細に説明する。
本発明で用いられる有機高分子粒子(A)は、分子内に水酸基およびカチオン性基の双方を有する有機高分子からなるものである。このような有機高分子からなる有機高分子粒子(A)を含有する塗料組成物によって形成された塗膜は、その表面に水酸基およびカチオン性基を有するため、高い親水性を有しており、これにより、優れた低摩擦性能を示す。本発明の塗料組成物によって形成された塗膜が優れた低摩擦性能を示すのは、塗膜表面に配置された水酸基と、該塗膜が浸漬される水とにより、塗膜表面上にヒドロゲルからなる層が形成され、これにより、塗膜表面の実質的な表面粗度が低減されることが一因であると考えられる。
(i)重量平均粒子径が10μm以上の有機高分子粒子(A)を用いることにより、上記したヒドロゲル層が、塗膜表面全体にわたって形成されやすくなり、その結果、優れた低摩擦性能が付与される。
(ii)重量平均粒子径が35μmを超える有機高分子粒子を用いると、35μm以下の有機高分子粒子(A)を用いる場合と比較して、有機高分子粒子の粗粒により表面粗度が増加し、その結果、低摩擦性能が阻害される。
(i)有機高分子粒子(A)の含有量を0.5重量%以上とすることにより、上記したヒドロゲル層が、塗膜表面全体にわたってより形成されやすくなり、その結果、優れた低摩擦性能をより長期にわたって得ることができる。
(ii)有機高分子粒子(A)の含有量を5.0重量%以下に抑えることにより、5.0重量%を超える量の有機高分子粒子(A)を用いる場合と比較して、有機高分子粒子中の粗粒による粗度増加の影響が抑制されるため、その結果、優れた低摩擦性能をより長期にわたって得ることができる。
本発明の塗料組成物は、バインダー樹脂としての基体樹脂(B)を含有する。本発明の塗料組成物に含有される基体樹脂(B)は、下記一般式(1):
-COO-M-OCO-A (1)
(式中、Mは、2価以上の金属であり、Aは、一塩基酸の有機酸残基を表す。)
で示される基、あるいは、下記一般式(2):
-COO-Si(R1R2R3) (2)
(式中、R1、R2およびR3は、同一または異なって、イソプロピル基またはn-ブチル基を表す。)
で示される基の少なくともいずれかを側鎖に有するか、または、主鎖間を架橋する下記一般式(3):
-COO-M-OCO- (3)
(式中、Mは、上記と同じ意味を表す。)
で示される架橋構造を有する樹脂を含む。なかでも、安定した低摩擦効果を長期にわたって維持できることから、上記一般式(1)および/または上記一般式(2)で示される基を側鎖に有するアクリル樹脂、ならびにポリマー主鎖間を架橋する上記一般式(3)で示される架橋構造を有するアクリル樹脂が好ましく用いられる。
(I)上記一般式(1)で示される基を側鎖に有するアクリル樹脂(以下、アクリル樹脂(I)と称する)、
(II)上記一般式(1)で示される基と上記一般式(2)で示される基とを側鎖に有するアクリル樹脂(以下、アクリル樹脂(II)と称する)、
(III)上記一般式(2)で示される基を側鎖に有するアクリル樹脂(以下、アクリル樹脂(III)と称する)、および、
(IV)ポリマー主鎖間を架橋する上記一般式(3)で示される架橋構造を有するアクリル樹脂(以下、アクリル樹脂(IV)と称する)。
アクリル樹脂(I)は、アクリル樹脂側鎖に、上記一般式(1)で表される基を少なくとも1つ有するアクリル樹脂である。アクリル樹脂(I)は、たとえば、下記方法(a)または(b)により製造することができる。
(a)重合性不飽和有機酸とその他の共重合可能な不飽和単量体とを共重合させて得られる樹脂に、金属化合物と一塩基酸とを反応させるか、または、一塩基酸の金属エステルを用いエステル交換させる方法、
(b)金属含有重合性不飽和単量体とその他の共重合可能な不飽和単量体とを共重合させる方法。
本発明において使用できる一塩基酸のうち、上記一塩基環状有機酸以外のものとしては、たとえば、酢酸、(メタ)アクリル酸、プロピオン酸、酪酸、ラウリル酸、パルミチン酸、2-エチルヘキサン酸、ステアリン酸、リノール酸、オレイン酸、クロル酢酸、フルオロ酢酸、吉草酸、バーサティック酸、12-ヒドロキシステアリン酸および水添ヒマシ油脂肪酸等の炭素数1~30程度の一塩基酸等を挙げることができる。好ましくは、炭素数5~20の一塩基酸である。これらの一塩基環状有機酸以外の一塩基酸は、単独で用いてもよく、2種以上を併用してもよい。また、一塩基酸として、一塩基環状有機酸と、一塩基環状有機酸以外の一塩基酸とを併用してもよい。
アクリル樹脂(II)は、アクリル樹脂側鎖に、上記一般式(1)で表される基と上記一般式(2)で示される基をそれぞれ少なくとも1つ有するアクリル樹脂である。
(c)重合性不飽和有機酸と、上記一般式(4)で示されるトリオルガノシリル(メタ)アクリレートと、その他の共重合可能な不飽和単量体とを重合させる第一の工程、および、第一の工程により得られた樹脂に金属化合物と一塩基酸とを反応させるか、または、一塩基酸の金属エステルを用いエステル交換させる第二の工程からなる方法、
(d)金属含有重合性不飽和単量体と、上記一般式(4)で示されるトリオルガノシリル(メタ)アクリレートと、その他の共重合可能な不飽和単量体とを共重合する方法。
アクリル樹脂(III)は、アクリル樹脂側鎖に、上記一般式(2)で表される基を少なくとも1つ有するアクリル樹脂であり、上記アクリル樹脂(I)および(II)と同様、自己研磨型ポリマーである。
アクリル樹脂(IV)は、ポリマー主鎖間を架橋する上記一般式(3)で示される架橋構造を少なくとも1つ有するアクリル樹脂である。上記一般式(3)において、Mは、2価以上の金属を表し、好ましくは、Mg、Zn、Ca等の2価の金属である。
〔(CH2=CHCOO)2M〕 (5)
(式中、Mは、Mg、Zn、Ca等の2価の金属を表す。)
および、下記一般式(6):
〔(CH2=C(CH3)COO)2M〕 (6)
(式中、Mは、Mg、Zn、Ca等の2価の金属を表す。)
で表される2個の不飽和基を有する金属含有重合性単量体等を挙げることができる。
本発明の塗料組成物は、塗膜の物性や塗膜の消耗速度を調整するために、上記基体樹脂(B)とともに、その他のバインダー樹脂を含有していてもよい。その他のバインダー樹脂としては、特に限定されないが、たとえば、塩化ゴム、ポリ酢酸ビニル、アルキド樹脂、ポリエステル樹脂、ポリ塩化ビニル等を挙げることができる。また、その他のバインダー樹脂として、上記アクリル樹脂(I)~(IV)以外のアクリル樹脂が用いられてもよい。アクリル樹脂(I)~(IV)以外のアクリル樹脂としては、ポリ(メタ)アクリル酸アルキルエステルなどを挙げることができる。また、本発明の塗料組成物は、必要に応じて、シリコンオイル;ワックス;ワセリン;流動パラフィン;ロジン;水添ロジン;ナフテン酸;脂肪酸;ロジン、水添ロジン、ナフテン酸および脂肪酸の2価金属塩;塩素化パラフィン;ポリビニルアルキルエーテル;ポリプロピレンセバケート;部分水添ターフェニル;ならびにポリエーテルポリオール等の添加剤を含有していてもよい。その他のバインダー樹脂および添加剤は、それぞれ単独で使用しても2種以上を併用してもよい。
本発明の塗料組成物には、たとえば、防汚剤、可塑剤、顔料、溶剤等の慣用の添加剤を添加することができる。
(製造例1:樹脂溶液Aの調製)
冷却管、温度計、攪拌機、窒素導入管、デカンターを備えた4つ口フラスコに、イソプロピルアルコール20g、プロピレングリコールメチルエーテル110gおよび酸化亜鉛22gを加え80℃に加熱した。メタクリル酸22gおよびナフテン酸(MW=300、AV(酸価)=165)75gを2時間にわたり滴下し2時間保温した。ついで、この溶液中の溶剤を、減圧下、75℃で除去することにより、上記一般式(1)で示される基を有する重合性単量体の濃度が50.4重量%である単量体溶液を得た。
冷却管、温度計、攪拌機、窒素導入管を備えた4つ口フラスコに、キシレン80gおよびn-ブタノール20gを加え100℃に加熱した。この溶液に、アクリル酸エチル40g、アクリル酸18g(0.25M)、アクリル酸シクロヘキシル15g、メタクリル酸メトキシポリエチレングリコール(n=9)27gおよびt-ブチルパーオキシ2-エチルヘキサノエート1.5gの混合溶液を3時間にわたり滴下し、その後3時間保温して樹脂溶液aを得た。
冷却管、温度計、攪拌機、窒素導入管を備えた4つ口フラスコに、キシレン100gを加え100℃に加熱した。この溶液に、メタクリル酸メチル40g、メタクリル酸トリ-i-プロピルシリル55g、メタクリル酸2-メトキシエチル5gおよびt-ブチルパーオキシ2-エチルヘキサノエート1.5gの混合溶液を3時間にわたり滴下し、その後3時間保温して、固形分濃度50.7重量%の樹脂溶液Cを得た。この樹脂溶液Cは、基体樹脂として、上記一般式(2)で示される基を側鎖に有するアクリル樹脂を含有するものである。
冷却管、温度計、攪拌機、窒素導入管を備えた4つ口フラスコに、キシレン50gおよびn-ブタノール40gを加え100℃に加熱した。この溶液に、メタクリル酸メチル20g、アクリル酸エチル40g、ジアクリル酸亜鉛15g、ナフテン酸亜鉛アクリル酸25gおよびt-ブチルパーオキシ2-エチルヘキサノエート1.2gの混合溶液を4時間にわたり滴下した。滴下終了30分後に、t-ブチルパーオキシ2-エチルヘキサノエート0.3gおよびキシレン10gを30分にわたり滴下し、その後2時間保温して、固形分濃度50.4重量%の樹脂溶液Dを得た。この樹脂溶液Dは、基体樹脂として、Znを含有する架橋構造を有するアクリル樹脂を含有するものである。
冷却管、温度計、攪拌機、窒素導入管、デカンターを備えた4つ口フラスコに、イソプロピルアルコール20g、プロピレングリコールメチルエーテル110gおよび酸化銅21.5g(0.25M)を加え80℃に加熱した。メタクリル酸22g(0.25M)、ナフテン酸(MW=300、AV(酸価)=165)75gを2時間にわたり滴下し2時間保温した。ついで、この溶液中の溶剤を、減圧下、75℃で除去することにより、上記一般式(1)で示される基を有する重合性単量体の濃度が50.4重量%である単量体溶液を得た。
冷却管、温度計、攪拌機、窒素導入管を備えた4つ口フラスコに、キシレン50gおよびn-ブタノール40gを加え100℃に加熱した。この溶液に、メタクリル酸メチル20g、アクリル酸エチル40g、ジアクリル酸亜鉛25g、アクリル酸イソブチル15gおよびt-ブチルパーオキシ2-エチルヘキサノエート1.2gの混合溶液を4時間にわたり滴下した。滴下終了30分後に、t-ブチルパーオキシ2-エチルヘキサノエート0.3gおよびキシレン10gを30分にわたり滴下し、その後2時間保温して、固形分濃度50.3重量%の樹脂溶液Fを得た。この樹脂溶液Fは、基体樹脂として、Znを含有する架橋構造を有するアクリル樹脂を含有するものである。
冷却管、温度計、攪拌機、窒素導入管を備えた4つ口フラスコに、キシレン90gを加え100℃に加熱した。この溶液に、メタクリル酸メチル10g、アクリル酸エチル32g、メタクリル酸トリ-i-プロピルシリル40g、アクリル酸18gおよびt-ブチルパーオキシ2-エチルヘキサノエート1.2gの混合溶液を2時間にわたり滴下した。滴下終了30分後に、t-ブチルパーオキシ2-エチルヘキサノエート0.3gおよびキシレン10gを30分にわたり滴下し、その後3時間保温した。この溶液に、ロジン80g、酢酸銅29.7gおよびキシレン200gを加え、生成する酢酸を除去しながら、8時間反応させた。その後、キシレンを加え、固形分濃度52重量%の樹脂溶液Gを得た。この樹脂溶液Gは、基体樹脂として、上記一般式(1)で示される基と上記一般式(2)で示される基とを側鎖に有するアクリル樹脂を含有するものである。
上記製造例2で得られた樹脂溶液a 200gに、ナフテン酸(AV(酸価)=200)70g、酢酸銅38g、キシレン200gを加え、生成する酢酸を除去しながら、8時間反応させた。その後、キシレンを加え、固形分濃度51重量%の樹脂溶液Hを得た。この樹脂溶液Hは、基体樹脂として、上記一般式(1)で示される基を側鎖に有するアクリル樹脂を含有するものである。
上記製造例2で得られた樹脂溶液a 200gに、ナフテン酸(AV(酸価)=165)85g、酢酸亜鉛34gおよびキシレン200gを加え、生成する酢酸を除去しながら、8時間反応させた。その後、キシレンを加え、固形分濃度55重量%の樹脂溶液Iを得た。この樹脂溶液Iは、基体樹脂として、上記一般式(1)で示される基を側鎖に有するアクリル樹脂を含有するものである。
(製造例10~19)
キチン(大日本精化工業社製)をジェット粉砕機で粉砕し、重量平均粒子径が、それぞれ1、5、10、20、35および50μmであるキチンからなる有機高分子粒子(以下、それぞれ有機高分子粒子I~VIと称する)を得た。同様に、キトサン(大日本精化工業社製)をジェット粉砕機で粉砕し、重量平均粒子径が、それぞれ5、15、30および60μmであるキトサンからなる有機高分子粒子(以下、それぞれ有機高分子粒子VII~Xと称する)を得た。なお、有機高分子粒子の重量平均粒子径は、(株)島津製作所製「レーザ回折式粒度分布測定装置 SALD-2200」を用いて測定した(分散媒:エタノール、測定温度:25℃)。
ER-20(旭電化社製ノニオン系乳化剤)70gとポリビニルアリルアミン(数平均分子量25000)20gとイオン交換水300gとからなる水溶液に、メタクリル酸メチル50g、メタクリル酸10g、メタクリル酸2-エチルヘキシル75g、アクリル酸シクロヘキシル20g、エチレングリコールジメタクリレート7gおよび過硫酸カリウム8gからなる溶液を加えた後、攪拌機を用いて乳化させ、懸濁液Aを得た。
ER-20(旭電化社製ノニオン系乳化剤)60gとイオン交換水300gとからなる水溶液に、メタクリル酸メチル50g、メタクリル酸2-エチルヘキシル75g、アクリル酸シクロヘキシル20g、エチレングリコールジメタクリレート20gおよびアゾビスイソブチロニトリル8gからなる溶液を加えた後、攪拌機を用いて乳化させ、懸濁液B(粒径15μm)を得た。
ER-20(旭電化社製ノニオン系乳化剤)40gとポリビニルアリルアミン(数平均分子量25000)20gとイオン交換水300gとからなる水溶液に、メタクリル酸メチル50g、メタクリル酸2-エチルヘキシル70g、メタクリル酸2-ヒドロキシエチル5g、アクリル酸シクロヘキシル20g、エチレングリコールジメタクリレート20gおよびアゾビスイソブチロニトリル8gからなる溶液を加えた後、攪拌機を用いて乳化させ、懸濁液C(粒径18μm)を得た。
表1および表2に示される配合組成に従い、各配合成分をディスパーを用いてガラスビーズで分散し、塗料組成物を調製した。表1および表2における配合量の数値の単位はすべて「g」である。なお、使用した防汚剤a~hは、以下のとおりである。得られた塗料組成物について以下の評価を行なった。
防汚剤a:ジンクジメチルジチオカーバメート
防汚剤b:N-(フルオロジクロロメチルチオ)フタルイミド
防汚剤c:3-ヨード-2-プロペニルブチルカーバメート
防汚剤d:ピリジン-トリフェニルボラン
防汚剤e:ロダン銅
防汚剤f:亜酸化銅
防汚剤g:ジンクピリチオン
防汚剤h:銅ピリチオン
(摩擦抵抗試験)
直径10cm、高さ10cmの塩ビ製円筒ドラムに、得られた塗料組成物を塗布し、乾燥させて塗膜を形成した後、海水中で回転させ(周速度換算で約10ノット)、トルクメーターにより摩擦抵抗を測定した。バフ処理によって鏡面仕上げした平滑な塩ビ製円筒ドラムの摩擦抵抗を標準として測定し、それぞれの摩擦抵抗の増減を表1および表2に示した。海水浸漬直後(初期)、および、1ヶ月浸漬後の摩擦抵抗を評価した。表1および表2に示される「摩擦抵抗係数」とは、以下の式により算出される値である。
「摩擦抵抗係数」=[(各塗料組成物を塗布したときの摩擦抵抗)-(標準摩擦抵抗)]/(標準摩擦抵抗)×100(%)
船舶の航行におけるエネルギー消費原単位(単位生産額当たりのエネルギー消費を意味し、当該原単位が大きくなると、所謂、燃費が悪くなる。)は、航行抵抗に比例する。したがって、摩擦抵抗係数の低下率に相応したエネルギー消費原単位の削減を得ることができる。
10cm×30cmのアクリル板に、得られた塗料組成物を乾燥膜厚が約200μmとなるように塗布し、二昼夜、室温で乾燥させ試験塗膜板を得た。その後、岡山県玉野市日本ペイントマリン株式会社の臨海研究所の筏で浸漬試験を12ヶ月間実施した。当該試験を実施した後の、試験塗膜板への生物の付着を目視で評価した。評価結果を表1および表2に示す。
B;フジツボ、イガイ、藻類等の大型生物が付着した。
10cm×30cmのアクリル板に、得られた塗料組成物を乾燥膜厚が約200μmとなるように塗布し、二昼夜、室温で乾燥させ試験塗膜板を得た。その後、岡山県玉野市日本ペイントマリン株式会社の臨海研究所の筏で、一週間浸漬し、3日間乾燥させた。この浸漬と乾燥とを5回繰り返した後、塗膜のクラックの有無を目視で評価した。評価結果を表1および表2に示す。
B;クラックが発生。
(A)重量平均粒子径が5μmである有機高分子粒子IIを配合した比較例2と、重量平均粒子径が10μmである有機高分子粒子IIIを配合した実施例1とを比較すると、実施例1では、初期および1ヵ月後の摩擦抵抗係数が2倍以上小さくなっており、これらの粒子径を境に、低摩擦性能が顕著に向上する。
(B)重量平均粒子径が35μmである有機高分子粒子Vを配合した実施例3と、重量平均粒子径が50μmである有機高分子粒子VIを配合した比較例3とを比較すると、実施例3では、初期および1ヵ月後の摩擦抵抗係数が30倍以上小さくなっており、これらの粒子径を境に、低摩擦性能が顕著に向上する。
(C)一方、重量平均粒子径が1および5μmである有機高分子粒子IおよびIIをそれぞれ配合した比較例1および2は、有機高分子粒子を配合していない比較例7と比較して、摩擦抵抗係数は若干低減されるものの、重量平均粒子径が10~35μmの場合ほど顕著なものではない。また、比較例1と比較例2を比較すると、両者の摩擦抵抗係数に実質的な差はない。
(D)塗料固形分中の有機高分子粒子の含有量が0.4重量%である比較例5と、有機高分子粒子の含有量が0.5重量%である実施例4とを比較すると、実施例4では、特に、1ヵ月後の摩擦抵抗係数が5倍以上小さくなっており、これらの含有量を境に、1ヵ月後における低摩擦性能が顕著に向上する。
(E)塗料固形分中の有機高分子粒子の含有量が5.0重量%である実施例7と、有機高分子粒子の含有量が6.7重量%である比較例6とを比較すると、実施例7では、特に、1ヵ月後の摩擦抵抗係数が3倍小さくなっており、これらの含有量を境に、1ヵ月後における低摩擦性能が顕著に向上する。
表3に示される配合組成に従い、各配合成分をディスパーを用いてガラスビーズで分散し、塗料組成物を調製した。表3における配合量の数値の単位はすべて「g」である。また、使用した防汚剤d~hは、上述のとおりである。得られた塗料組成物について、実施例1~16および比較例1~11と同様にして評価を行なった。評価結果を表3に示す。
Claims (9)
- 分子内に水酸基およびカチオン性基を有する有機高分子からなり、重量平均粒子径が10~35μmである有機高分子粒子(A)と、
下記一般式(1):
-COO-M-OCO-A (1)
(式中、Mは、2価以上の金属であり、Aは、一塩基酸の有機酸残基を表す。)
で示される基、あるいは、
下記一般式(2):
-COO-Si(R1R2R3) (2)
(式中、R1、R2およびR3は、同一または異なって、イソプロピル基またはn-ブチル基を表す。)
で示される基の少なくともいずれかを側鎖に有するか、または、
主鎖間を架橋する下記一般式(3):
-COO-M-OCO- (3)
(式中、Mは、前記と同じ意味を表す。)
で示される架橋構造を有する基体樹脂(B)と、
を含有し、
前記有機高分子粒子(A)の含有量は、塗料固形分中、0.5~5.0重量%である塗料組成物。 - 前記カチオン性基は、アミノ基またはアミド基である、請求の範囲第1項に記載の塗料組成物。
- 前記有機高分子は、キチン、キトサンおよびこれらの誘導体からなる群から選択される少なくとも1種である、請求の範囲第2項に記載の塗料組成物。
- 前記基体樹脂(B)は、前記一般式(1)で示される基を側鎖に有するアクリル樹脂を含む、請求の範囲第1項に記載の塗料組成物。
- 前記基体樹脂(B)は、前記一般式(1)または(2)の少なくともいずれかを側鎖に有し、かつ、主鎖間を架橋する前記一般式(3)で示される架橋構造を有する樹脂を含む、請求の範囲第1項に記載の塗料組成物。
- 分子内に水酸基およびカチオン性基を有する有機高分子からなり、重量平均粒子径が10~35μmである有機高分子粒子(A)と、
下記一般式(1):
-COO-M-OCO-A (1)
(式中、Mは、2価以上の金属であり、Aは、一塩基酸の有機酸残基を表す。)
で示される基、あるいは、
下記一般式(2):
-COO-Si(R1R2R3) (2)
(式中、R1、R2およびR3は、同一または異なって、イソプロピル基またはn-ブチル基を表す。)
で示される基の少なくともいずれかを側鎖に有するか、または、
主鎖間を架橋する下記一般式(3):
-COO-M-OCO- (3)
(式中、Mは、前記と同じ意味を表す。)
で示される架橋構造を有する基体樹脂(B)とを、前記有機高分子粒子(A)の含有量が、塗料固形分中、0.5~5.0重量%となるように混合する工程を備える、塗料組成物の製造方法。 - 請求の範囲第1項に記載の塗料組成物によって形成された塗膜。
- 請求の範囲第1項に記載の塗料組成物によって形成された塗膜を有する水中構造物。
- 請求の範囲第1項に記載の塗料組成物によって形成された塗膜を有する船舶。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6257464A (ja) | 1985-05-17 | 1987-03-13 | Nippon Paint Co Ltd | 金属含有樹脂組成物 |
WO2005116155A1 (ja) | 2004-05-26 | 2005-12-08 | Nippon Paint Co., Ltd. | 塗料組成物、塗膜及び水中摩擦低減方法 |
JP2006328244A (ja) | 2005-05-26 | 2006-12-07 | Nippon Paint Co Ltd | 複合樹脂粒子の製造方法、複合樹脂粒子及び塗料組成物 |
JP2007169628A (ja) | 2005-11-25 | 2007-07-05 | Nippon Paint Co Ltd | 塗料組成物、塗膜、水中摩擦低減方法及び塗料組成物の製造方法 |
JP2007169449A (ja) * | 2005-12-21 | 2007-07-05 | Nippon Paint Co Ltd | 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 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6727304B2 (en) * | 2000-06-28 | 2004-04-27 | Mitsubishi Rayon Co., Ltd. | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
GB2435602B (en) * | 2004-12-28 | 2010-11-24 | Nippon Paint Co Ltd | Hydraulic stain-proof coating composition, stain-proof coating film and underwater structure |
JP2006182955A (ja) | 2004-12-28 | 2006-07-13 | Nippon Paint Co Ltd | 水性硬化型防汚塗料組成物、防汚性塗膜及び水中構造物 |
US20070059273A1 (en) * | 2005-09-15 | 2007-03-15 | Price Ronald R | Novel biodegradable biofouling control coating and method of formulation |
DE102006008535A1 (de) | 2006-02-22 | 2007-08-30 | Stiftung Nano Innovations - For A Better Living, Olten | Anitbakterielle Beschichtungszusammensetzung auf Basis eines Siliziumdioxid erzeugenden Mittels, ein Anwendungsset, eine nanoskalige Beschichtung, die Herstellung der Beschichtung, die Weiterverarbeitung der Beschichtung sowie deren Verwendung |
-
2009
- 2009-09-24 TW TW098132350A patent/TWI440673B/zh active
- 2009-09-28 CN CN2009801382212A patent/CN102165026A/zh active Pending
- 2009-09-28 US US13/120,608 patent/US8575232B2/en active Active
- 2009-09-28 JP JP2010531840A patent/JP5341902B2/ja active Active
- 2009-09-28 KR KR1020157011708A patent/KR102004020B1/ko active IP Right Grant
- 2009-09-28 WO PCT/JP2009/066747 patent/WO2010038692A1/ja active Application Filing
- 2009-09-28 EP EP09817725.6A patent/EP2336257B1/en active Active
- 2009-09-28 KR KR1020117009715A patent/KR20110063577A/ko active Application Filing
- 2009-09-28 BR BRPI0919540-8A patent/BRPI0919540B1/pt active IP Right Grant
- 2009-09-28 CN CN201510603453.8A patent/CN105176257B/zh active Active
- 2009-09-28 KR KR1020187002003A patent/KR20180010342A/ko not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6257464A (ja) | 1985-05-17 | 1987-03-13 | Nippon Paint Co Ltd | 金属含有樹脂組成物 |
WO2005116155A1 (ja) | 2004-05-26 | 2005-12-08 | Nippon Paint Co., Ltd. | 塗料組成物、塗膜及び水中摩擦低減方法 |
JP2006328244A (ja) | 2005-05-26 | 2006-12-07 | Nippon Paint Co Ltd | 複合樹脂粒子の製造方法、複合樹脂粒子及び塗料組成物 |
JP2007169628A (ja) | 2005-11-25 | 2007-07-05 | Nippon Paint Co Ltd | 塗料組成物、塗膜、水中摩擦低減方法及び塗料組成物の製造方法 |
JP2007169449A (ja) * | 2005-12-21 | 2007-07-05 | Nippon Paint Co Ltd | 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 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2336257A4 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011241260A (ja) * | 2010-05-14 | 2011-12-01 | Mitsubishi Rayon Co Ltd | 金属含有共重合体の製造方法 |
US20150118405A1 (en) * | 2010-06-23 | 2015-04-30 | Nippon Paint Marine Coatings Co., Ltd. | Method of forming antifouling coating film |
US9695324B2 (en) * | 2010-06-23 | 2017-07-04 | Nippon Paint Marine Coatings Co., Ltd. | Method of forming antifouling coating film |
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JP2012117019A (ja) * | 2010-12-03 | 2012-06-21 | Tottori Univ | キチンナノファイバーまたはキトサンナノファイバーを含む塗料組成物 |
WO2014142035A1 (ja) * | 2013-03-13 | 2014-09-18 | 株式会社エステン化学研究所 | 水または海水との摩擦抵抗の小さい防汚塗膜 |
JPWO2014142035A1 (ja) * | 2013-03-13 | 2017-02-16 | 株式会社エステン化学研究所 | 水または海水との摩擦抵抗の小さい防汚塗膜 |
JP2015040533A (ja) * | 2013-08-23 | 2015-03-02 | 水ing株式会社 | 空気抜き孔を有するポンプ及び排水ポンプ装置 |
WO2016063789A1 (ja) * | 2014-10-22 | 2016-04-28 | 日東化成株式会社 | 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 |
JPWO2016063789A1 (ja) * | 2014-10-22 | 2017-08-31 | 日東化成株式会社 | 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 |
JP2016089167A (ja) * | 2014-10-31 | 2016-05-23 | 中国塗料株式会社 | 防汚塗料組成物、防汚塗膜および防汚基材、ならびに防汚基材の製造方法 |
JP2016210881A (ja) * | 2015-05-08 | 2016-12-15 | 三菱レイヨン株式会社 | 防汚塗料用樹脂組成物および防汚塗膜 |
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EP2336257B1 (en) | 2014-08-27 |
EP2336257A1 (en) | 2011-06-22 |
BRPI0919540A2 (pt) | 2020-09-01 |
KR20180010342A (ko) | 2018-01-30 |
JP5341902B2 (ja) | 2013-11-13 |
TW201022378A (en) | 2010-06-16 |
CN105176257B (zh) | 2018-12-14 |
EP2336257A4 (en) | 2012-07-11 |
TWI440673B (zh) | 2014-06-11 |
KR102004020B1 (ko) | 2019-07-25 |
BRPI0919540B1 (pt) | 2021-06-08 |
CN105176257A (zh) | 2015-12-23 |
JPWO2010038692A1 (ja) | 2012-03-01 |
CN102165026A (zh) | 2011-08-24 |
US20110178204A1 (en) | 2011-07-21 |
US8575232B2 (en) | 2013-11-05 |
KR20110063577A (ko) | 2011-06-10 |
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