WO2019216413A1 - Composition de revêtement antisalissure, film de revêtement antisalissure, matériau de base revêtu d'un film de revêtement antisalissure et procédé antisalissure - Google Patents

Composition de revêtement antisalissure, film de revêtement antisalissure, matériau de base revêtu d'un film de revêtement antisalissure et procédé antisalissure Download PDF

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Publication number
WO2019216413A1
WO2019216413A1 PCT/JP2019/018744 JP2019018744W WO2019216413A1 WO 2019216413 A1 WO2019216413 A1 WO 2019216413A1 JP 2019018744 W JP2019018744 W JP 2019018744W WO 2019216413 A1 WO2019216413 A1 WO 2019216413A1
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Prior art keywords
antifouling
antifouling coating
mass
coating film
group
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PCT/JP2019/018744
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English (en)
Japanese (ja)
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聡一郎 谷野
淳内 筏井
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中国塗料株式会社
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Priority to JP2020518357A priority Critical patent/JP7082659B2/ja
Priority to KR1020207032105A priority patent/KR102544292B1/ko
Priority to CN201980031693.1A priority patent/CN112105697A/zh
Publication of WO2019216413A1 publication Critical patent/WO2019216413A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to an antifouling coating composition, an antifouling coating film formed using the same, a substrate with an antifouling coating, a method for producing the same, and an antifouling method.
  • antifouling paints containing hydrolyzable polymers having the property of renewing the coating film from the surface in water are widely used.
  • An antifouling coating using such a hydrolyzable polymer as a binder becomes hydrophilic from the surface as the hydrolysis progresses in water, and the hydrophilized portion is cleaned by a water stream to exhibit coating renewability.
  • silyl ester polymers having a trialkylsilyl ester group as a hydrolyzable group are widely used.
  • Antifouling coating compositions using such silyl ester polymers have been studied for a long time, and various further studies for improving antifouling properties have been conducted so far.
  • Patent Document 1 contains a polymer having a silyl ester group and a polymer having a structure in which a quaternary ammonium group and / or a quaternary phosphonium group neutralized with a conjugate base of sulfonic acid is bonded to the main chain. Adhesion inhibiting coating compositions have been proposed.
  • an antifouling coating composition using a silyl ester-based copolymer including the antifouling coating composition disclosed in Patent Document 1 is an environment that is affected by sunlight and gravity in water, for example, typically On the bilge keel upper surface provided between the ship bottom vertical part or the ship bottom vertical part and the flat part of the ship, fouling by plants is likely to occur, and in particular, there is a problem that the antifouling property against moss is inferior.
  • an object of the present invention is to provide an antifouling coating composition capable of exhibiting antifouling performance even in the above environment.
  • an object of this invention is to provide the antifouling coating film formed from the said antifouling coating composition, the base material with an antifouling coating film, its manufacturing method, and the antifouling method.
  • the gist of the present invention is as follows.
  • the present invention relates to the following [1] to [15].
  • the silyl ester copolymer (A) contains a structural unit derived from a silyl (meth) acrylate represented by the following formula (I), and is 100 masses of all structural units of the silyl ester copolymer.
  • the antifouling paint composition according to [1], wherein the content of the structural unit derived from the silyl (meth) acrylate represented by the formula (I) with respect to parts is 40 parts by mass or more and 80 parts by mass or less.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 , R 3 and R 4 each independently represents a monovalent hydrocarbon group.
  • R 31 represents a monovalent hydrocarbon group, and a represents an integer of 1 or more and 5 or less.
  • R 24 represents a hydrogen atom or a methyl group
  • R 25 represents a monovalent hydrocarbon group
  • R 26 represents a divalent hydrocarbon group
  • s is an integer of 1 to 30. Is shown.
  • the content of the structural unit derived from the compound represented by the formula (V) with respect to 100 parts by mass of all the structural units of the silyl ester copolymer (A) is 5 parts by mass or more and 40 parts by mass or less.
  • the antifouling paint composition according to one.
  • the content of the sulfonic acid group-containing compound (B) in the solid content of the antifouling coating composition is 0.01% by mass or more and 7% by mass or less.
  • the antifouling paint composition according to one.
  • an antifouling paint composition capable of exhibiting excellent antifouling performance against moss in an environment affected by sunlight and gravity in water. Furthermore, according to this invention, the antifouling coating film formed from the said antifouling paint composition, the base material with an antifouling coating film, its manufacturing method, and the antifouling method can be provided.
  • the antifouling coating composition of the present invention (hereinafter also simply referred to as “coating composition”) is selected from the group consisting of a silyl ester copolymer (A), a sulfonic acid compound, and a sulfonic acid polymer. At least one sulfonic acid group-containing compound (B).
  • the antifouling coating composition which exhibits the antifouling performance excellent with respect to moss in the environment which receives the influence of sunlight and gravity in water can be provided.
  • the detailed action mechanism by which said effect is acquired is not necessarily clear, a part is estimated as follows. That is, with the progress of hydrolysis of the silyl ester group in water, the antifouling coating film containing the silyl ester copolymer (A) forms a hydrophilic surface layer film called a hydrolyzed layer. On the surface affected by sunlight and gravity, there is a tendency that moss grows easily in this hydrolyzed layer due to the efficiency of photosynthesis and the promotion of seed adhesion.
  • the coating film contains the sulfonic acid group-containing compound (B)
  • the thickness of the hydrolyzed layer tends to be kept thin, so that it is considered to have excellent antifouling performance against moss.
  • each component contained in the antifouling coating composition of the present invention will be described in detail.
  • the antifouling coating composition of the present invention contains a silyl ester copolymer (A).
  • the silyl ester copolymer (A) is a copolymer having a silyl ester group in its chemical structure, preferably (i) silyl (meth) acrylate (a1), and optionally (ii) It is a copolymer having a structural unit derived from another monomer (a2).
  • the silyl ester copolymer (A) is preferably a copolymer that does not substantially have a structural unit derived from the sulfonic acid group-containing monomer (a3).
  • a copolymer having a structural unit derived from A means a copolymer in which the monomer compound A is introduced by a polymerization reaction or a chain transfer reaction. Therefore, when the monomer compound A has a mercaptoalkyl group, the radical polymerization terminal pulls out the hydrogen atom of the mercaptoalkyl group (R—SH), and the generated R—S ⁇ (sulfur radical) starts polymerization.
  • the silyl ester copolymer (A) has a constitutional unit derived from the monomer compound. .
  • each structural unit of the silyl ester copolymer (A) will be described.
  • Silyl (meth) acrylate (a1) is a monomer represented by the following formula (I).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 , R 3 and R 4 each independently represents a monovalent hydrocarbon group.
  • R 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving the long-term antifouling property and water resistance of the antifouling coating film.
  • R 2 , R 3 and R 4 each independently represent a monovalent hydrocarbon group, and as such a hydrocarbon group, a linear, branched or cyclic alkyl group, and An aryl group etc. are mentioned.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • R 2 , R 3 and R 4 are each independently a methyl group, an ethyl group, from the viewpoint of imparting appropriate hydrolyzability to the antifouling coating film to improve long-term antifouling properties and water resistance. It is preferably selected from isopropyl, n-propyl, sec-butyl, n-butyl, and phenyl, and all of R 2 , R 3 and R 4 are isopropyl, n-propyl, sec-butyl. It is more preferably a group or an n-butyl group, and it is still more preferable that all of R 2 , R 3 and R 4 are isopropyl groups.
  • silyl (meth) acrylate (a1) trialkylsilyl (meth) acrylate, alkyldiarylsilyl (meth) acrylate, and aryldialkylsilyl (meth) acrylate are preferable, and trialkylsilyl (meth) acrylate is more preferable.
  • Triisopropylsilyl (meth) acrylate is particularly preferred, and triisopropylsilyl methacrylate is most preferred from the viewpoint of improving the internal water resistance of the antifouling coating film to be formed.
  • the silyl ester copolymer (A) may have a structural unit derived from two or more different silyl (meth) acrylates (a1).
  • the structural unit derived from silyl (meth) acrylate (a1) becomes the same structure as the structural unit derived from (meth) acrylic acid by hydrolyzing. Therefore, in the silyl ester copolymer (A), a part of the structural unit derived from the silyl (meth) acrylate (a1) has the same structure as the structural unit derived from (meth) acrylic acid by hydrolysis. May be. Moreover, this structural unit produced by hydrolysis may react with other components, such as a metal oxide which an antifouling coating composition contains, and may form metal ester further.
  • the total amount of the structural units derived from the silyl (meth) acrylate (a1) with respect to 100 parts by mass of all the structural units of the silyl ester copolymer (A) is a viewpoint of making the water resistance of the antifouling coating film good, And from the viewpoint of forming a coating film having an appropriate hydrolysis rate in water, preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 30 parts by mass or more and 80 parts by mass or less, and further preferably 40 parts by mass or more and 80 parts by mass. Part or less, more preferably 40 parts by mass or more and 70 parts by mass or less, and particularly preferably 45 parts by mass or more and 65 parts by mass or less.
  • the ratio of each content (mass) of the structural unit derived from each monomer in the silyl ester copolymer (A) is sufficient to suppress hydrolysis of the silyl ester copolymer (A).
  • the respective monomers It can be regarded as the same as the ratio of the charged amount (mass) of the reaction raw material.
  • the silyl ester copolymer (A) or a decomposition product thereof is analyzed by mass spectrometry, IR (infrared spectroscopy), NMR, ICP-MS (inductively coupled plasma mass spectrometer), ICP-AES (induction).
  • mass spectrometry IR (infrared spectroscopy), NMR, ICP-MS (inductively coupled plasma mass spectrometer), ICP-AES (induction).
  • IR infrared spectroscopy
  • NMR nuclear magnetic resonance
  • ICP-MS inductively coupled plasma mass spectrometer
  • ICP-AES induction
  • the silyl ester copolymer (A) preferably has a structural unit derived from the other monomer (a2).
  • the other monomer (a2) is a monomer excluding the silyl (meth) acrylate (a1) and is a monomer copolymerizable with the silyl (meth) acrylate (a1).
  • the other monomer (a2) preferably does not contain a sulfonic acid group-containing monomer (a3) described later.
  • the organosiloxane-containing monomer (a21) and / or alkoxyalkyl (meth) acrylate or aryloxyalkyl (meth) acrylate (a22) are used. It is preferable to have an alkyl (meth) acrylate or aryl (meth) acrylate (a23) from the viewpoint of improving the coating strength, It is preferable to have unsaturated carboxylic acid (a26) from a viewpoint of improving the crack resistance after the antifouling coating film is immersed in seawater.
  • organosiloxane-containing monomer (a21) The organosiloxane-containing monomer (a21) has a structure represented by the following formula (II).
  • R 11 , R 12 and R 13 each independently represent a monovalent hydrocarbon group
  • X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group
  • m and n are each independently 0 or more
  • p and q are each independently 0 or 1
  • n + p + q is 1 or more.
  • R 11 , R 12 , and R 13 each independently represent a monovalent hydrocarbon group, and examples thereof include the same groups as R 2 , R 3 , and R 4 .
  • an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable.
  • each X independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and a (meth) acryloyloxyalkyl group is preferred from the viewpoint of uniform polymerization, and the viscosity of the polymer to be formed Mercaptoalkyl groups are also preferred from the standpoint of reducing the amount and facilitating handling.
  • the (meth) acryloyloxyalkyl group in X is represented by the following formula (III).
  • R 21 represents a hydrogen atom or a methyl group
  • R 22 represents an alkylene group
  • * represents the bonding position with Si to which the (meth) acryloyloxyalkyl group is bonded
  • R 22 represents an alkylene group, and the alkylene group may be linear or branched, and the alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, from the viewpoint of reactivity. Hereinafter, it is more preferably 2 or more and 4 or less.
  • the mercaptoalkyl group in X is represented by the following formula (IV).
  • R 23 represents an alkylene group, and * represents a bonding position with Si to which the mercaptoalkyl group is bonded.
  • R 23 represents an alkylene group, and the alkylene group may be linear or branched, and the alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, from the viewpoint of reactivity. Hereinafter, it is more preferably 2 or more and 4 or less.
  • X in the formula (II) is a 2- (meth) acryloyloxyethyl group, 3- (meth) acryloyloxypropyl group, 4- (meth) acryloyloxybutyl group, mercaptomethyl group, 2-mercaptoethyl group, Examples include 2-mercaptopropyl group, 3-mercaptopropyl group, 4-mercaptobutyl group and the like.
  • m and n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.
  • m and n mean the average added mole number of (SiR 12 2 O) and (SiXR 13 O), respectively.
  • M + n in the formula (II) is preferably 2 or more. That is, the compound represented by formula (II) preferably has a polyorganosiloxane moiety.
  • this specification when two or more different repeating units are described in parallel between [], these repeating units are respectively repeated in any form and order of random, alternating or block. Indicates that it may be.
  • a silyl ester type copolymer (A) has the structural unit derived from the compound (a211) whose n is 0, p is 1, and q is 0 in Formula (II). It is preferable.
  • the antifouling coating composition containing the silyl ester copolymer (A) having a structural unit derived from such a compound (a211) is particularly capable of forming an antifouling coating film having excellent antifouling properties.
  • m is preferably 3 or more and 200 or less, and more preferably 5 or more and 70 or less from the viewpoint of ease of polymerization.
  • a commercially available product can be used.
  • Shin-Etsu Chemical X-22-174ASX single terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 900 g / mol
  • KF-2012 single terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 4,600 g, manufactured by Kog
  • the silyl ester copolymer (A) may have a structural unit derived from the compound (a212) in which n is 0 and p and q are 1 in the formula (II). preferable.
  • the antifouling coating composition containing the silyl ester copolymer (A) having a structural unit derived from such a compound (a212) is preferable in that the top coat adhesion of the formed coating film is good.
  • m is preferably 3 or more and 200 or less, and more preferably 5 or more and 70 or less from the viewpoint of ease of polymerization.
  • a commercially available product can be used.
  • Shin-Etsu Chemical X-22-164 both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 190 g / mol
  • X-22-164AS both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 450 g, manufactured by Kogyo Co., Ltd.
  • X-22-164A both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 860 g / mol
  • X-22-164B both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 1630 g / mol
  • X -22-164C both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 2,370 g / mol
  • X-22-164E both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 3,900 g / mol
  • X-22-167B both terminal mercaptoalkyl-modified organopolysiloxane, functional group equivalent 1,670 g / mol).
  • a silyl ester type copolymer (A) has a structural unit derived from the compound (a213) whose n is 1 or more in a formula (II).
  • n is preferably from 1 to 30.
  • a commercially available product can be used.
  • KF-2001 side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent 1,900 g / mol
  • KF-2004 side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent of 30,000 g / mol
  • the silyl ester copolymer (A) has a structural unit derived from the organosiloxane-containing monomer (a21), the content of the structural unit is the antifouling performance under the alternating dry and wet conditions of the antifouling coating film. From the viewpoints of water resistance and substrate adhesion, it is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more, with respect to 100 parts by mass of all the structural units of the silyl ester copolymer (A). 30 parts by mass or less, more preferably 1.5 parts by mass or more and 15 parts by mass or less.
  • alkoxyalkyl (meth) acrylate or aryloxyalkyl (meth) acrylate (a22) includes those represented by the following formula (V). preferable.
  • R 24 represents a hydrogen atom or a methyl group
  • R 25 represents a monovalent hydrocarbon group
  • R 26 represents a divalent hydrocarbon group
  • s is an integer of 1 to 30. Is shown.
  • R 24 represents a hydrogen atom or a methyl group, preferably a hydrogen atom from the viewpoint of ease of polymerization, and preferably a methyl group from the viewpoint of water resistance of the coating film to be formed.
  • R 25 represents a monovalent hydrocarbon group, and examples thereof include an alkyl group and an aryl group.
  • the monovalent hydrocarbon group for R 25 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms from the viewpoint of the stability of the antifouling coating composition and the physical properties of the coating film to be formed.
  • R 26 represents a divalent hydrocarbon group, and examples thereof include an alkylene group.
  • the alkylene group is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.
  • s represents an integer of 1 or more and 30 or less, preferably 1 or more and 15 or less, more preferably 1 or more and 6 or less, and still more preferably 1.
  • the coating film formed by the antifouling coating composition containing the silyl ester copolymer (A) is imparted with appropriate hydrophilicity, and the antifouling coating has excellent water resistance. It is preferable because a film can be obtained.
  • a monomer (a22) may be used individually by 1 type, may use 2 or more types together, and may contain both an alkoxyalkyl (meth) acrylate and an aryloxyalkyl (meth) acrylate. Good.
  • the silyl ester copolymer (A) has a structural unit derived from the monomer (a22), from the viewpoint of antifouling performance, water resistance and hardness of the antifouling coating film, the content of the structural unit is , Preferably 5 parts by weight or more and 40 parts by weight or less, more preferably 10 parts by weight or more and 35 parts by weight or less, and still more preferably 15 parts by weight with respect to 100 parts by weight of all the structural units of the silyl ester copolymer (A) The amount is 30 parts by mass or less.
  • alkyl (meth) acrylate or aryl (meth) acrylate (a23) The alkyl group in the alkyl (meth) acrylate or aryl (meth) acrylate (a23) (hereinafter also simply referred to as “monomer (a23)”) may be linear, branched or cyclic. , Preferably an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the aryl group is preferably 6 to 14 carbon atoms, More preferred is an aryl group having 6 to 10 carbon atoms.
  • methyl methacrylate is preferable from the viewpoint of obtaining an antifouling coating film excellent in coating film strength and thus excellent in antifouling performance
  • butyl acrylate is preferable from the viewpoint of excellent water resistance and crack resistance of the antifouling coating film.
  • a monomer (a23) may be used individually by 1 type, and may use 2 or more types together.
  • the monomer (a23) may contain both alkyl (meth) acrylate and aryl (meth) acrylate.
  • the content of the structural unit is 100 parts by mass of all the structural units of the silyl ester copolymer (A). On the other hand, it is preferably 0.2 to 40 parts by mass, more preferably 1 to 35 parts by mass, and still more preferably 3 to 30 parts by mass.
  • the silyl ester copolymer (A) has a structural unit derived from methyl methacrylate, the content of the structural unit is preferably based on 100 parts by mass of all the structural units of the silyl ester copolymer (A).
  • the silyl ester copolymer (A) has a structural unit derived from butyl acrylate, the content of the structural unit is preferably based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). Is 0.2 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 3 to 10 parts by mass.
  • hydroxyalkyl (meth) acrylate (a24) examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( And (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • a monomer (a24) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the monomer (a24) is preferably 0.5 with respect to 100 parts by weight of all the structural units of the silyl ester copolymer (A). It is 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less.
  • silycidyl (meth) acrylate (a25) examples include at least one selected from glycidyl acrylate and glycidyl methacrylate.
  • the silyl ester copolymer (A) has a structural unit derived from the monomer (a25), the content of the structural unit is based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). Preferably, it is 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 15 parts by mass.
  • the unsaturated carboxylic acid (a26) (hereinafter also simply referred to as “monomer (a26)”) is a monomer having a carboxy group in the molecule.
  • the monomer (a26) include (meth) acrylic acid, (meth) acryloyloxyalkyl succinic acid, (meth) acryloyloxyalkylphthalic acid, (meth) acryloyloxyalkyl hexahydrophthalic acid, itaconic acid, maleic acid , Maleic anhydride, itaconic acid, crotonic acid, 6-acrylamidohexanoic acid, and the like, and (meth) acrylic acid is preferred from the viewpoint of handling and availability of the compound and the viscosity of the polymer obtained by polymerization.
  • silyl ester copolymer (A) has a structural unit derived from the monomer (a26), a part of the silyl ester copolymer (A) and other components such as a metal oxide in a process such as the preparation of an antifouling coating composition React A metal ester group or a metal salt may be formed.
  • the silyl ester copolymer (A) has a structural unit derived from the monomer (a26)
  • the content of the structural unit is based on 100 parts by mass of all the structural units of the silyl ester copolymer (A).
  • the amount is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less.
  • the metal ester group-containing unsaturated monomer (a27) (hereinafter also simply referred to as “monomer (a27)”) is a single monomer having a metal ester group formed by bonding a metal and a carboxylic acid. Refers to the body.
  • the “polyvalent metal ester group” or “divalent metal ester group” to be described later refers to a group formed by combining a polyvalent metal or divalent metal with a carboxylic acid.
  • the metal ester group is preferably a polyvalent metal ester group, more preferably a divalent metal ester group represented by the following formula (VI).
  • M is a divalent metal, and a divalent metal can be appropriately selected from the metals described above. Among these, M is preferably a Group 10-12 metal such as nickel, copper, and zinc, more preferably selected from the group consisting of copper and zinc, and zinc is even more preferable.
  • the monomer (a27) include zinc di (meth) acrylate, copper di (meth) acrylate, zinc acrylate (methacrylic acid), copper acrylate (methacrylic acid), and di (3-acryloyloxypropionic acid.
  • the silyl ester copolymer (A) has a structural unit derived from the monomer (a27), the content of the structural unit is based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). Preferably, it is 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 15 parts by mass.
  • vinyl compound (a28) examples include styrene, ⁇ -methylstyrene, vinyl acetate, vinyl benzoate, vinyl toluene, acrylonitrile, vinyl pyridine, vinyl pyrrolidone, vinyl chloride and the like.
  • Another vinyl compound (a28) may be used individually by 1 type, and may use 2 or more types together.
  • the silyl ester copolymer (A) of the present invention does not substantially contain a structural unit derived from the sulfonic acid group-containing monomer (a3).
  • “substantially free” means that the content is 0.1% by mass or less.
  • the sulfonic acid-containing monomer (a3) is a monomer containing a sulfonic acid group, and examples thereof include vinyl sulfonic acid, styrene sulfonic acid, 3- (methacryloyloxy) propane sulfonic acid, and 2- (meth) acrylamide. Examples include -2-methylpropane sulfonic acid.
  • the silyl ester copolymer (A) has a structural unit derived from the other monomer (a2), the structural unit derived from the silyl (meth) acrylate (a1) and the other monomer (a2)
  • the mass ratio [(a1) / (a2)] to the structural unit derived from is preferably 10/90 or more and 90/10 or less, more preferably 40/60 or more and 80/20 or less, and further preferably 45/55 or more. 70/30 or less, particularly preferably 45/55 or more and 65/35 or less.
  • the said mass ratio [(a1) / (a2)] can be computed from the preparation ratio of each monomer at the time of manufacturing a copolymer.
  • the silyl ester copolymer (A) can be produced, for example, by the following procedure.
  • a solvent is charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube and a heating / cooling jacket, and heated and stirred under a temperature of 80 ° C. to 90 ° C. in a nitrogen stream.
  • the monomer (a1) and optionally the monomer (a2), and a mixed liquid of a polymerization initiator, a chain transfer agent, and a solvent are dropped into the reaction vessel from the dropping device.
  • a silyl ester type copolymer (A) can be obtained by performing a polymerization reaction.
  • a polymerization initiator which can be used for manufacture of a silyl ester type copolymer (A) Various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2′-azobis (isobutyronitrile) [AIBN], 2,2 Azo series such as' -azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], 4,4'-azobis-4-cyanovaleric acid Compounds, and tert-butyl peroctoate [TBPO].
  • benzoyl peroxide hydrogen peroxide
  • cumene hydroperoxide tert-butyl hydroperoxide
  • potassium persulfate sodium persulfate
  • AIBN 2,2′-azobis (isobuty
  • These polymerization initiators may be used alone or in combination of two or more. These radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added to the reaction system both at the start of the reaction and during the reaction.
  • the amount of the polymerization initiator used in the production of the silyl ester copolymer (A) is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the respective monomers (reaction raw materials). 0.5 parts by mass or more and 5 parts by mass or less are more preferable.
  • the chain transfer agent that can be used in the production of the silyl ester copolymer (A) is not particularly limited, and examples thereof include ⁇ -methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, ⁇ -terpinene; tert-dodecyl; Mercaptans such as mercaptan and n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; and the like. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together. When using a chain transfer agent in manufacture of a silyl ester type copolymer (A), the usage-amount is 0.1 to 5 mass parts with respect to a total of 100 mass parts of said each monomer (reaction raw material). The following is preferred.
  • Solvents that can be used in the production of the silyl ester copolymer (A) include, for example, aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene; propanol, butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl Examples include alcohol solvents such as ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; ester solvents such as ethyl acetate and butyl acetate; and water.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene
  • propanol, butanol propylene glycol monomethyl ether
  • dipropylene glycol monomethyl examples include alcohol solvents such as ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amy
  • the weight average molecular weight (Mw) of the silyl ester copolymer (A) is preferably 3,000 or more and 70,000 or less from the viewpoint of coating workability of the coating composition and the strength of the antifouling coating film. More preferably, it is 10,000 or more and 50,000 or less.
  • the weight average molecular weight (Mw) of a silyl ester-type copolymer (A) points out the value of the gel permeation chromatography (GPC) measured by the method as described in an Example.
  • the polydispersity (Mw / Mn) of the silyl ester copolymer (A) is not particularly limited, but is preferably 20 or less, more preferably 10 or less, from the viewpoint of obtaining a uniform coating composition.
  • the content of the silyl ester copolymer (A) in the antifouling coating composition of the present invention is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 35% in the solid content of the coating composition. It is 10 mass% or less, More preferably, it is 10 mass% or more and 20 mass% or less.
  • the above content is preferable as the total content of the silyl ester copolymers (A). The same applies to each component described later.
  • the antifouling coating composition of the present invention contains at least one sulfonic acid group-containing compound (B) selected from the group consisting of a sulfonic acid compound and a sulfonic acid polymer.
  • the sulfonic acid compound is a compound having one or more sulfonic acid groups in the molecule, and means a sulfonic acid group-containing compound other than the sulfonic acid polymer.
  • the sulfonic acid compound has a repeating unit in the molecule. Means a low molecular weight compound.
  • the sulfonic acid polymer is a polymer having at least one sulfonic acid group in the molecule, and excludes the silyl ester copolymer (A).
  • a part or all of the sulfonic acid group may form a salt.
  • the antifouling coating composition of the present invention contains the sulfonic acid group-containing compound (B), an antifouling coating film having good moss resistance can be formed even in the surface affected by sunlight and gravity in water. . Furthermore, when the antifouling coating composition contains an imidazole compound (C) described later, it is possible to suppress a decrease in storage stability and to improve the antistaining coating composition.
  • the sulfonic acid group-containing compound (B) may be a sulfonic acid compound or a sulfonic acid polymer, but the antifouling coating composition has a low viscosity and is excellent in coating workability and in storage stability. From the viewpoint, a sulfonic acid compound is preferable.
  • the sulfonic acid compound is not particularly limited as long as it has one or more sulfonic acid groups in the molecule.
  • methanesulfonic acid trifluoromethanesulfonic acid, ethanesulfonic acid, vinylsulfonic acid, 1-propanesulfonic acid, etc.
  • aromatic sulfonic acid compounds include aromatic sulfonic acid compounds, benzene sulfonic acid, alkylbenzene sulfonic acid, diphenyl sulfonic acid, naphthalene sulfonic acid, and other aromatic sulfonic acid compounds.
  • an aromatic sulfonic acid compound is preferable from the viewpoint of forming an antifouling coating film excellent in moss resistance on the surface affected by sunlight and gravity in water, and a compound represented by the following formula (VII) It is more preferable that
  • R 31 represents a monovalent hydrocarbon group, and a represents an integer of 1 or more and 5 or less.
  • R 31 represents a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group include a linear, branched, or cyclic alkyl group, an aryl group, and the like, and some or all of the hydrogen atoms bonded to the carbon atom are nitrogen, oxygen, sulfur, It may be substituted by a substituent containing a heteroatom such as halogen, and a heteroatom such as nitrogen, oxygen or sulfur may be interposed between the carbon-carbon bonds of the hydrocarbon group.
  • the substituent containing a hetero atom and the hetero atom interposed between the carbon-carbon bonds may be one kind or two or more kinds.
  • a represents an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, more preferably 1.
  • R 31 When a plurality of R 31 are present, they may be the same or different. Among these, from the viewpoint of availability and the like, monoalkylbenzenesulfonic acid in which a in Formula (VII) is 1 and the monovalent hydrocarbon group in R 31 is an alkyl group is preferable. From the viewpoint of forming an antifouling coating film having excellent storage stability when used in combination with an imidazole compound (C) described later, R 31 is preferably an alkyl group having 2 to 30 carbon atoms, and a linear alkyl group is A linear alkyl group having 10 to 18 carbon atoms is more preferable.
  • Examples of the monoalkylbenzenesulfonic acid include p-toluenesulfonic acid, m-xylene-4-sulfonic acid, cumenesulfonic acid (4-isopropylbenzenesulfonic acid), p-decylbenzenesulfonic acid, p-undecylbenzenesulfonic acid, Examples thereof include p-dodecylbenzenesulfonic acid, p-tridecylbenzenesulfonic acid, p-tetradecylbenzenesulfonic acid and the like.
  • sulfonic acid compounds can be used.
  • “Taca Power B120” branched monoalkylbenzene sulfonic acid, acid value 173 mgKOH / g
  • “Taca Power L121” linear mono
  • “Taika Power L124” linear monoalkyl benzene sulfonic acid, acid value 181 mg KOH / g
  • “Neopelex GS” manufactured by Kao Co., Ltd. 11 to 16 linear monoalkylbenzenesulfonic acid mixture, acid value 186 mgKOH / g).
  • the sulfonic acid polymer refers to a polymer containing a structural unit derived from a monomer having at least one sulfonic acid group in one molecule as a structural unit of the sulfonic acid polymer.
  • Monomers having a sulfonic acid group include styrene sulfonic acid, isoprene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, isoamylene sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, and methallyl. Examples thereof include sulfonic acid (2-methyl-2-propene-1-sulfonic acid) or a salt thereof.
  • the sulfonic acid polymer may contain a structural unit derived from a monomer other than the sulfonic acid group-containing monomer.
  • the monomer other than the sulfonic acid group-containing monomer include the monomer (a22) and the monomer (a23).
  • the sulfonic acid polymer include polystyrene sulfonic acid.
  • the sulfonic acid group-containing compound (B) any acid value can be used without limitation. However, in view of ease of handling and viscosity of the coating composition, an imidazole compound (C) described later is used in combination.
  • the acid value of the sulfonic acid group-containing compound (B) is preferably 100 mgKOH / g or more and 310 mgKOH / g or less. From the viewpoint of being able to form an antifouling coating film having excellent crack resistance when C) is used in combination, it is more preferably from 150 mgKOH / g to 200 mgKOH / g.
  • the sulfonic acid compound those having any molecular weight can be used without limitation.
  • the sulfonic acid compound is excellent in handling stability and the viscosity of the coating composition, and excellent in storage stability when used in combination with an imidazole compound (C) described later.
  • the molecular weight of the sulfonic acid compound is preferably 170 g / mol or more and 570 g / mol or less, and when the imidazole compound (C) described later is used in combination, an antifouling coating film excellent in crack resistance can be formed. From the viewpoint, it is more preferably 280 g / mol or more and 380 g / mol or less.
  • the weight average molecular weight (Mw) of the sulfonic acid polymer is preferably 3,000 or more and 100,000 or less, preferably 10,000 or more and 70,000 or less, from the viewpoint of coating workability of the coating composition. It is more preferable.
  • the content of the sulfonic acid group-containing compound (B) in the antifouling coating composition of the present invention is the solid content of the coating composition from the viewpoint of the coating workability of the coating composition and the water resistance of the antifouling coating film to be formed. , Preferably 0.01% to 7% by mass, more preferably 0.03% to 5% by mass, still more preferably 0.05% to 3% by mass, particularly preferably 0.1% by mass. The content is 2% by mass or less.
  • a sulfonic acid group containing compound (B) may be used individually by 1 type, and may use 2 or more types together. The sulfonic acid group-containing compound (B) may be used partially or completely neutralized.
  • neutralization in the sulfonic acid polymer may be performed as a monomer, or may be neutralized after the polymer is formed.
  • Examples of the base used for neutralization include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and amine compounds such as ammonia, triethanolamine and trimethylamine.
  • the salt of the sulfonic acid group-containing compound (B) is preferably an alkali metal salt, and more preferably a sodium salt.
  • the antifouling coating composition of the present invention comprises an imidazole compound (C), a monocarboxylic acid compound (D), other antifouling agent (E), other binder components (F), a pigment (G), an organic solvent (if necessary). H), an anti-sagging agent / anti-settling agent (I), a dehydrating agent (J), and a plasticizer (K) may be contained.
  • the antifouling coating composition of the present invention is for the purpose of appropriately adjusting the hydrolysis rate of the silyl ester copolymer (A) in water and the viewpoint of imparting good antifouling properties to the antifouling coating film to be formed.
  • the imidazole compound (C) may be contained. Examples of the imidazole compound (C) include 2-methylimidazole, 4-methylimidazole, 4,5-dimethyl-1H-imidazole, (+/ ⁇ )-4- [1- (2,3-dimethylphenyl) ethyl].
  • -1H-imidazole is preferred.
  • An imidazole compound (C) may be used individually by 1 type, and may use 2 or more types together.
  • (+/ ⁇ )-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole has optical isomerism, but even in the case of only one optical isomer, a mixture in an arbitrary ratio It may be.
  • an imidazolium salt with the sulfonic acid group-containing compound (B) or the like an imidduct to a metal or the like may be used, or an adduct to a metal or an imidazolium salt may be formed in the antifouling coating composition or antifouling coating film of the present invention.
  • the content thereof is preferably in the antifouling coating composition from the viewpoint of imparting good antifouling properties to the antifouling coating film to be formed.
  • the antifouling coating composition of the present invention contains an imidazole compound (C), the content thereof is such that the equivalent value EQ represented by the following formula is 0.00 relative to the sulfonic acid group-containing compound (B).
  • the content of 5 or more and 10 or less is preferable, and the content of 0.8 or more and 7 or less is more preferable.
  • EQ ⁇ W B ⁇ (56110 ⁇ AV) ⁇ ⁇ (W C ⁇ MW C ) (W B, AV each said sulfonic acid group-containing compound (content of B), and an acid value (mgKOH / g), W C , MW C indicates the content and the molecular weight of the imidazole compound (C).)
  • the antifouling coating composition of the present invention may contain a monocarboxylic acid compound (D).
  • the monocarboxylic acid compound (D) promotes the renewability of the antifouling coating film containing it from the surface in water, and the antifouling coating film contains an antifouling agent. Enhances the antifouling property of the antifouling coating by accelerating the release of the antifouling agent into water, and also has a function of imparting appropriate water resistance to the antifouling coating.
  • the antifouling coating composition contains the imidazole compound (C)
  • Examples of the monocarboxylic acid compound (D) include a compound in which one carboxy group is substituted for a saturated or unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms, or a saturated or unsaturated compound having 3 to 40 carbon atoms.
  • a compound obtained by substituting one carboxy group for the alicyclic hydrocarbon or a compound obtained by substituting one carboxy group for a modified aliphatic hydrocarbon or alicyclic hydrocarbon is preferred.
  • abietic acid neoabietic acid, dehydroabietic acid, parastrinic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexene carboxylic acid, versatic acid, stearic acid, naphthenic acid and the like are preferable.
  • rosins whose main components are abietic acid, parastrinic acid, isopimaric acid and the like.
  • rosins include rosins such as gum rosin, wood rosin and tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salts, and pine tar.
  • trimethylisobutenylcyclohexene carboxylic acid examples include a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which is 1,2,3-trimethyl- 5- (2-Methylprop-1-en-1-yl) cyclohex-3-en-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl)
  • the main component 85% by mass or more) of cyclohex-3-ene-1-carboxylic acid.
  • a monocarboxylic acid compound (D) may be used individually by 1 type, and may use 2 or more types together.
  • a part or all of the monocarboxylic acid compound (D) in the present invention may form a salt.
  • the salt of the monocarboxylic acid compound (D) include a zinc salt and a copper salt. Even if the salt is formed in advance before preparing the antifouling coating composition, other salts may be used at the time of preparing the antifouling coating composition. It may be formed by reaction with a paint component.
  • the content thereof is preferably 1% by mass or more and 50% by mass or less, more preferably 2% in the solid content of the antifouling coating composition.
  • the content is not less than 20% by mass and not more than 20% by mass, more preferably not less than 2.5% by mass and not more than 10% by mass, and particularly preferably not less than 3% by mass and not more than 5% by mass.
  • the content of the monocarboxylic acid (D) in the antifouling coating composition is determined based on the solid content of the silyl ester copolymer (A).
  • the antifouling coating composition of the present invention may contain an antifouling agent (E) other than the imidazole compound (C).
  • antifouling agents (E) include, for example, cuprous oxide, copper pyrithione, zinc pyrithione, copper thiocyanate (rodane copper), copper (metal copper), 4,5-dichloro-2-n-octyl-4- Isothiazolin-3-one (also known as DCOIT), 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as tralopyryl), borane-nitrogen base Adducts (pyridine triphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.), N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,
  • antifouling agents (E) may be used alone or in combination of two or more.
  • the antifouling agent (E) it is preferable to contain cuprous oxide (E1) from the viewpoint of improving the antifouling property of the antifouling coating film to be formed, especially the aquatic organisms of animal species, and water resistance.
  • the cuprous oxide (E1) preferably includes those having an average particle diameter of about 1 ⁇ m to 30 ⁇ m, and from the viewpoint of improving the antifouling property and water resistance of the antifouling coating film to be formed. Is more preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • the cuprous oxide (E1) is preferably surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil or the like from the viewpoint of long-term stability during storage. As such cuprous oxide (E1), commercially available products can be used.
  • NC-301 manufactured by NC Tech Co., Ltd., average particle size: 2 ⁇ m to 4 ⁇ m
  • NC-803 NC Tech Co., Ltd., average particle size: 6 ⁇ m or more and 10 ⁇ m or less
  • Red Cop97N Premium manufactured by AMERICA CHEMET Co.
  • Purple Cop manufactured by AMERICA CHEMET Co.
  • LoLoTint97 manufactured by AMERICAN CHEMET Co.
  • the coating composition contains cuprous oxide (E1)
  • the content is antifouling from the viewpoint of the coating workability of the antifouling coating composition in the present invention, the antifouling performance of the antifouling coating film, and the water resistance.
  • the solid content of the coating composition it is preferably 20% by mass to 80% by mass, more preferably 40% by mass to 70% by mass, and further preferably 50% by mass to 65% by mass.
  • the antifouling agents it is also preferable to contain copper pyrithione from the viewpoint of improving the antifouling property of the antifouling coating film to be formed, particularly on aquatic micro organisms.
  • the coating composition contains copper pyrithione
  • the content thereof is that of the antifouling coating composition from the viewpoint of the coating workability of the antifouling coating composition in the present invention and the antifouling performance and water resistance of the antifouling coating film.
  • solid content Preferably they are 0.5 mass% or more and 10 mass% or less, More preferably, they are 1 mass% or more and 5 mass% or less.
  • the antifouling agent may contain zinc pyrithione, DCOIT, tralopyryl, borane-nitrogen base adducts (pyridine triphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.). It is preferable in terms of excellent soiling.
  • the antifouling coating composition of the present invention is other than the silyl ester copolymer (A).
  • Other binder components (F) may be included.
  • the other binder component (F) include acrylic copolymers (acrylic resins), vinyl polymers, chlorinated paraffins, n-paraffins, terpene phenols, polyvinyl ethyl ethers, and the like.
  • Other binder components (F) may be used alone or in combination of two or more.
  • acrylic copolymer examples include copolymers obtained by polymerizing two or more selected from the other monomers (a2). From the standpoint of antifouling property, the monomers It is preferable to include a structural unit derived from (a22) or the metal ester group-containing unsaturated monomer (a26).
  • binder component (F) commercially available products may be used.
  • the other binder component (F) in the present invention in addition to the above, for example, a polymer (f1) containing two or more acid groups (hereinafter referred to as “acid groups” as described in International Publication No. 2014/010702). And a polymer obtained by reacting the monocarboxylic acid compound (D) with a metal compound.
  • acid groups as described in International Publication No. 2014/010702.
  • Examples of such an acid group-containing polymer (f1) include a polyester polymer (f11) and an acrylic polymer (f12), preferably a polyester polymer (f11).
  • Such a polyester polymer (f11) preferably has a solid content acid value of 50 mgKOH / g or more and 250 mgKOH / g or less, more preferably 80 mgKOH / g or more and 200 mgKOH / g or less.
  • Such a polyester polymer (f11) can be obtained by reaction of one or more polyhydric alcohols with one or more polyhydric carboxylic acids and / or anhydrides thereof, and any kind can be used in any quantity. The acid value and viscosity can be adjusted by the combination.
  • polyester-based polymer (f11) for example, a trivalent or higher alcohol (f111), a dibasic acid and / or its anhydride (f112), and a divalent alcohol (f113) are reacted. Thereafter, those obtained by further reacting an alicyclic dibasic acid and / or its anhydride (f114) are preferred.
  • the monocarboxylic acid compound (D) to be reacted with such a polyester polymer (f11) those described above can be used. Among them, rosins are preferably used.
  • the metal compound for example, zinc oxide And metal oxides such as cuprous oxide can be used, and zinc oxide is particularly preferable.
  • the antifouling coating composition of the present invention contains other binder component (F), the content thereof is preferably 1% by mass or more and 20% by mass or less in the solid content of the coating composition.
  • the antifouling coating composition of the present invention may contain the pigment (G) for the purpose of coloring the coating film or concealing the base, and for the purpose of adjusting to an appropriate coating film strength.
  • the pigment (G) include talc, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and zinc sulfide.
  • extender pigments petals (red iron oxide), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, phthalocyanine blue, etc. preferable. These pigments may be used alone or in combination of two or more.
  • the antifouling coating composition of the present invention contains the pigment (G), the content thereof is a desired viscosity depending on the hiding property required for the antifouling coating film to be formed, the coating form of the coating composition, and the like.
  • a preferable amount is determined depending on the solid content of the coating composition, but an amount of 1% by mass to 50% by mass is preferable.
  • the antifouling coating composition may contain an organic solvent (H) for the purpose of keeping the viscosity of the coating composition low and improving spray atomization.
  • organic solvent (H) aromatic hydrocarbon-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, ketone-based, ester-based, and alcohol-based organic solvents can be used, and preferably aromatic hydrocarbons.
  • Organic solvent examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, mesitylene and the like.
  • Examples of the aliphatic hydrocarbon organic solvent include pentane, hexane, heptane, and octane.
  • Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, ethylcyclohexane, and the like.
  • Examples of the ketone organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate.
  • Examples of the ester organic solvent include propylene glycol monomethyl ether acetate.
  • Examples of the alcohol organic solvent include isopropanol, n-butanol, propylene glycol monomethyl ether and the like.
  • An organic solvent (H) may be used individually by 1 type, and may use 2 or more types together.
  • the preferred content in the coating composition is determined by the desired viscosity according to the coating form of the coating composition, but preferably 0. It is 10 mass% or more and 40 mass% or less, More preferably, it is 20 mass% or more and 35 mass% or less. When there is too much content, malfunctions, such as a fall of sagging stop property, may generate
  • H organic solvent
  • the antifouling coating composition may contain a sagging inhibitor / antisettling agent (I).
  • Anti-sagging agents and anti-settling agents (I) include organic clay waxes (such as stearates and lecithin salts of Al, Ca and Zn), organic waxes (polyethylene wax, polyethylene oxide wax, amide wax (fatty acid amide, etc.) ), Polyamide wax, hydrogenated castor oil wax, etc.), a mixture of organic clay wax and organic wax, synthetic fine powder silica, and the like.
  • the anti-sagging agent / anti-settling agent (I) Commercially available products may be used as the anti-sagging agent / anti-settling agent (I).
  • the anti-sagging agent / anti-settling agent (I) may be used alone or in combination of two or more.
  • the antifouling coating composition of the present invention contains the anti-sagging agent / anti-settling agent (I), the content thereof is preferably 0.01% by mass or more and 10% by mass in the solid content of the antifouling coating composition.
  • the content thereof is preferably 0.1% by mass to 3% by mass, and still more preferably 0.5% by mass to 2% by mass.
  • the antifouling coating composition may contain a dehydrating agent (J) for the purpose of improving the storage stability of the coating composition.
  • a dehydrating agent (J) examples include alkoxysilane, zeolite known by the general name of “molecular sieve”, orthoester such as porous alumina and alkyl orthoformate, orthoboric acid, isocyanate and the like.
  • alkoxysilane is preferable from the viewpoint of easy availability and improved storage stability.
  • These dehydrating agents may be used alone or in combination of two or more.
  • the content thereof is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.00% in the solid content of the paint composition. It is 2 mass% or more and 2.5 mass% or less, More preferably, it is 0.5 mass% or more and 1.5 mass% or less.
  • the content of the dehydrating agent (J) is within the above range, the storage stability of the coating composition can be kept good.
  • the antifouling coating composition of the present invention may contain a plasticizer (K) for the purpose of imparting plasticity to the antifouling coating film.
  • a plasticizer (K) include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), and the like. These plasticizers may be used alone or in combination of two or more.
  • the antifouling coating composition of the present invention contains a plasticizer (K), the content thereof is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% in the solid content of the coating composition. It is from 5% by mass to 5% by mass. When the content of the plasticizer (K) is within the above range, the plasticity of the antifouling coating film can be kept good.
  • Each of the antifouling paint compositions of the present invention can be prepared using the same devices, means, etc. as those of known general antifouling paints. Specifically, after preparing the silyl ester copolymer (A), a solution of this polymer, the sulfonic acid group-containing compound (B), and other additives as required, at a time, or It can be produced by sequentially adding, stirring and mixing. Other additives may be mixed in advance in any combination, and in particular when the antifouling coating composition of the present invention contains an imidazole compound (C), the imidazole compound (C) is added to the coating composition. It is preferable to previously mix the sulfonic acid group-containing compound (B).
  • the antifouling coating film of the present invention is formed from the antifouling coating composition, and is preferably obtained by drying the antifouling coating composition.
  • the antifouling method of the present invention uses the above-mentioned antifouling coating film, and by providing the antifouling coating film on various substrates using the antifouling coating composition of the present invention. It is a method of antifouling.
  • the antifouling coating film can be obtained by applying the antifouling coating composition of the present invention on a coating film or a substrate and then drying it.
  • Examples of the method for applying the coating composition of the present invention include known methods such as a method using a brush, a roller, and a spray.
  • the antifouling coating composition applied by the above-described method is dried, for example, by leaving it at 25 ° C. for about 0.5 to 14 days, more preferably for about 1 to 7 days, to obtain a coating film. be able to.
  • the antifouling coating composition may be dried while blowing air under heating.
  • the thickness of the antifouling coating film of the present invention after drying is arbitrarily selected according to the renewal rate of the antifouling coating film, the period of use, and the like, but is preferably about 30 ⁇ m to 1,000 ⁇ m, for example.
  • the coating composition is preferably applied in a thickness of 10 ⁇ m to 300 ⁇ m, more preferably 30 ⁇ m to 200 ⁇ m, once to multiple times per application. Is mentioned.
  • the substrate with an antifouling coating film of the present invention is one in which the substrate is coated with the antifouling coating film formed from the antifouling coating composition, and has the antifouling coating film on the substrate It is.
  • the substrate with an antifouling coating film of the present invention can be produced by forming the antifouling coating film on the substrate by the method as described above.
  • the method for producing a substrate with an antifouling coating film of the present invention is not particularly limited. For example, a step of applying or impregnating the antifouling coating composition of the present invention to a substrate to obtain an applied body or an impregnated body (1-1 ) And a process (1-2) for drying the coated body or impregnated body.
  • the above-described application method can be employed as a method for applying the coating composition to the substrate.
  • the above-described application method can carry out by immersing a base material in the coating composition of sufficient quantity for making it impregnate.
  • limiting in particular in the method of drying the said application body or an impregnation body It can dry by the method similar to the method at the time of manufacturing an antifouling coating film.
  • the substrate with an antifouling coating film of the present invention comprises a step (2-1) of forming an antifouling coating film by drying the antifouling coating composition of the present invention, and the coating film applied to the substrate. It can also be obtained by the production method having the step (2-2).
  • the method for forming the coating film in the step (2-1) and the coating film can be manufactured by the same method as that used in manufacturing the antifouling coating film.
  • the method of applying the coating film to the substrate in the step (2-2) and for example, it can be applied by the method described in JP2013-129724A.
  • the antifouling paint composition of the present invention can be used to maintain the antifouling property of a substrate over a long period of time in a wide range of industrial fields such as ships, fisheries and marine structures.
  • base materials include, for example, ships (container ships, large steel ships such as tankers, fishing boats, FRP ships, wooden ships, yachts and other hull outer plates, these new ships or repair ships), fishing materials (ropes) , Fishing nets, fishing gear, floats, buoys, etc.), oil pipelines, water conduits, circulating water pipes, diver suits, underwater glasses, oxygen cylinders, bathing suits, torpedoes, underwater structures such as thermal / nuclear power plant outlets, seabeds Examples include cables, seawater use equipment (seawater pumps, etc.), mega floats, bay roads, submarine tunnels, harbor facilities, and various structures for marine civil engineering works in canals and waterways.
  • the base material is preferably selected from the group consisting of ships, underwater structures, and fishery materials, more preferably selected from the group consisting of ships and underwater structures, and may be a ship. Further preferred.
  • the base material on which the antifouling coating film of the present invention is formed on the surface is a surface treated with another processing agent such as an antirust agent, or a coating film such as a primer already formed on the surface.
  • the antifouling coating composition of the present invention may be overcoated on the surface already coated, and the type of the coating film with which the antifouling coating film of the present invention is in direct contact is not particularly limited. Absent.
  • the antifouling coating film of the present invention prevents moss that is likely to grow in an environment that is affected by sunlight and gravity in water, such as a ship bottom vertical part or a bilge keel upper surface provided between a ship bottom vertical part and a flat part. Excellent soiling.
  • solid content of each component used in the examples refers to a component excluding volatile components contained as a solvent in each component, and is obtained by drying each component in a hot air dryer at 108 ° C. for 3 hours. Is regarded as a solid content.
  • the viscosity of the copolymer solutions (A-1) to (A-4), the number average molecular weight (Mn), and the weight average molecular weight (Mw) of the copolymer contained therein are measured as follows. ⁇ Viscosity of copolymer solution> The viscosity of the copolymer solution at 25 ° C. was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • the area occupied by the mossy deposit on the test surface is less than 1% of the whole 4: The above-mentioned area is 1% or more and less than 10% of the whole 3: The above-mentioned area is 10% or more and less than 40% of the whole 2: The above-mentioned area is 40% or more and less than 70% of the whole 1: Same area as above 70% or more of the whole
  • the antifouling coating composition can form a coating film having excellent moss resistance, and even when it contains an imidazole compound (C).
  • Antifouling paint composition excellent in storage stability, antifouling coating film using the same, base material with antifouling coating film having the same on substrate, method for producing substrate with antifouling coating, and An antifouling method using the antifouling coating film can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne : une composition de revêtement antisalissure qui est capable de présenter d'excellentes performances antisalissure sur des bryophytes dans un environnement sous-marin recevant la lumière du soleil et soumis à la gravité ; un film de revêtement antisalissure ; un matériau de base revêtu d'un film de revêtement antisalissure ; un procédé de production d'un matériau de base revêtu d'un film de revêtement antisalissure ; et un procédé antisalissure. Une composition de revêtement antisalissure qui contient (A) un copolymère d'ester de silyle et (B) au moins un composé contenant un groupe acide sulfonique (à l'exclusion du copolymère d'ester de silyle (A)), qui est choisi dans le groupe constitué des composés d'acide sulfonique et des polymères d'acide sulfonique ; un film de revêtement antisalissure qui est formé de cette composition de revêtement antisalissure ; un matériau de base revêtu d'un film de revêtement antisalissure, qui est recouvert par ce film de revêtement antisalissure ; un procédé de production de ce matériau de base revêtu d'un film de revêtement antisalissure ; et un procédé antisalissure qui utilise ce film de revêtement antisalissure.
PCT/JP2019/018744 2018-05-11 2019-05-10 Composition de revêtement antisalissure, film de revêtement antisalissure, matériau de base revêtu d'un film de revêtement antisalissure et procédé antisalissure WO2019216413A1 (fr)

Priority Applications (3)

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JP2020518357A JP7082659B2 (ja) 2018-05-11 2019-05-10 防汚塗料組成物、防汚塗膜、防汚塗膜付き基材及び防汚方法
KR1020207032105A KR102544292B1 (ko) 2018-05-11 2019-05-10 방오 도료 조성물, 방오 도막, 방오 도막 부착 기재 및 방오 방법
CN201980031693.1A CN112105697A (zh) 2018-05-11 2019-05-10 防污涂料组合物、防污涂膜、带有防污涂膜的基材和防污方法

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JP2018092318 2018-05-11

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KR (1) KR102544292B1 (fr)
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Publication number Priority date Publication date Assignee Title
GB202107159D0 (en) 2021-03-23 2021-06-30 Jotun As Monitoring a vessel
WO2021180588A2 (fr) 2020-03-09 2021-09-16 Jotun A/S Robot de nettoyage de coque
WO2022200430A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance de la propreté d'une surface immergée d'un objet stationnaire

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JPH03166272A (ja) * 1989-11-24 1991-07-18 Dainippon Ink & Chem Inc 防汚塗料用樹脂組成物
JPH05504365A (ja) * 1989-12-22 1993-07-08 コートールズ　コーティングス（ホールディングス）　リミテッド 汚染物付着防止被覆組成物
JPH07102193A (ja) * 1993-09-30 1995-04-18 Nippon Oil & Fats Co Ltd 塗料組成物
JPH10182310A (ja) * 1996-12-24 1998-07-07 Katayama Chem Works Co Ltd 持続性水中防汚剤
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WO2009001829A1 (fr) * 2007-06-26 2008-12-31 Chugoku Marine Paints, Ltd. Composition de revêtement anti-tâche contenant un composé de triphénylbore à stabilité améliorée, ensemble d'agent anti-tâche utilisé pour celui-ci et un procédé de suppression/commande de la décomposition du composé de triphénylbore
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JP2017535637A (ja) * 2014-10-28 2017-11-30 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ シリルエステル基を含むポリマー、及び四級アンモニウム／ホスホニウムスルホネート基を含むポリマーを含む付着抑制被覆組成物
JP2017538802A (ja) * 2014-10-28 2017-12-28 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ シリルエステル官能基及び四級アンモニウム基／ホスホニウム基を含むポリマーを含む付着抑制組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021180588A2 (fr) 2020-03-09 2021-09-16 Jotun A/S Robot de nettoyage de coque
GB202107159D0 (en) 2021-03-23 2021-06-30 Jotun As Monitoring a vessel
WO2022200430A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance de la propreté d'une surface immergée d'un objet stationnaire
WO2022200427A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance d'un navire

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CN112105697A (zh) 2020-12-18
KR20200140358A (ko) 2020-12-15

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