CN113444418B - Antifouling coating composition - Google Patents

Antifouling coating composition Download PDF

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Publication number
CN113444418B
CN113444418B CN202110317954.5A CN202110317954A CN113444418B CN 113444418 B CN113444418 B CN 113444418B CN 202110317954 A CN202110317954 A CN 202110317954A CN 113444418 B CN113444418 B CN 113444418B
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antifouling
mass
coating film
meth
acrylate
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CN113444418A (en
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岩田雄树
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Chugoku Marine Paints Ltd
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Chugoku Marine Paints Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • 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
    • 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
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper

Abstract

The invention provides an antifouling coating composition which can form an antifouling coating film with excellent crack resistance, adhesiveness to a deteriorated coating film and dynamic antifouling property, and contains a silicone polymer and medetomidine. The antifouling paint composition comprises: a silicone-based polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a 1) represented by the formula (a 1), an acrylic-based polymer (B) having a structural unit (B-1) derived from glycidyl (meth) acrylate, medetomidine (C), and a specific amount of cuprous oxide (D), R 1 －CH＝C(CH 3 )－COO－(SiR 2 R 3 O) n －SiR 4 R 5 R 6 … (a 1) in the formula (a 1), R 2 ～R 6 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms, which may have a heteroatom. n is an integer of 0 or 1 or more. R is R 1 Is a hydrogen atom or R 7 -O-C (=o) -a group represented by R 7 Hydrogen atom, etc.

Description

Antifouling coating composition
Technical Field
The present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating film, and a method for producing a substrate with an antifouling coating film.
Background
Various aquatic organisms easily adhere to the surfaces of substrates (supply and drainage pipes for sea water in ships, structures in water, fishing nets, factories, etc.) exposed to water (sea, river, lake, etc.) for a long period of time in natural environments. If aquatic organisms adhere to the surface of the substrate, the appearance may be impaired or various problems may occur. For example, when the substrate is a ship, there are cases where the speed of the ship is reduced or the burnup is increased due to an increase in resistance caused by water flow. When the substrate is an underwater structure, there is a case where the anticorrosive coating film applied to the surface of the substrate is damaged, and there is a case where the strength and the function are lowered and the life is remarkably shortened. When the base material is a fishing net such as a culture net or a fixed net, the net is clogged with aquatic organisms, and there are cases where serious problems such as hypoxia death of the culture organisms and the captured organisms occur. When aquatic organisms adhere to and multiply on supply and drainage pipes of seawater in factories, firepower, nuclear power plants and the like, the supply and drainage pipes may be blocked or the flow rate may be reduced.
In order to prevent the adhesion of aquatic organisms causing such problems, an operation of forming an antifouling coating film by applying an antifouling paint to the surface of a substrate is generally performed. Among such antifouling paints, hydrolysis type antifouling paints are widely used from the viewpoint of their excellent antifouling performance, and as one of them, development of an antifouling paint containing a silicone polymer has been conducted.
Patent document 1 describes an antifouling coating composition containing a silicone copolymer containing triisopropylsilyl methacrylate and a hydrophilic (meth) acrylate comonomer, and medetomidine.
Patent document 2 describes an antifouling paint composition obtained by blending a copolymer containing a structural unit derived from styrene and a structural unit derived from glycidyl (meth) acrylate into an antifouling paint containing a silicone-based polymer.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2019-535868
Patent document 2: international publication No. 2014/175246
Disclosure of Invention
Technical problem to be solved by the invention
Patent document 1 discloses that the antifouling coating composition can form a coating film having cracking resistance and excellent antifouling properties, particularly excellent barnacle adhesion inhibition properties. However, in the examples of this document, the barnacle resistance was evaluated as the antifouling performance by the static immersion test, but the dynamic antifouling performance was not clear. Further, as a result of studies by the inventors of the present invention, it has been found that an antifouling coating film formed from an antifouling coating composition containing medetomidine is difficult to form an antifouling coating film excellent in both of crack resistance, adhesion to a conventional antifouling coating film deteriorated by immersion in seawater or the like (hereinafter, also simply referred to as a deteriorated coating film), and dynamic antifouling property. Further, it is found that the above-mentioned antifouling coating composition has room for improvement from the viewpoint of long-term storage stability.
The present invention aims to provide an antifouling paint composition containing a silicone polymer and medetomidine, which can form an antifouling coating film excellent in crack resistance, adhesion to a deteriorated coating film, and dynamic antifouling properties.
Technical scheme for solving technical problems
The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the antifouling paint composition described below can solve the above-mentioned problems. That is, the present invention relates to the following [1] to [10].
[1] An antifouling coating composition comprising: the antifouling paint composition comprises a silicone polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a 1) represented by the formula (a 1), an acrylic polymer (B) having a structural unit (B-1) derived from glycidyl (meth) acrylate, medetomidine (C), and cuprous oxide (D), wherein the content of the cuprous oxide (D) is more than 0 mass% and not more than 55 mass% in the solid content of the antifouling paint composition.
R 1 －CH＝C(CH 3 )－COO－(SiR 2 R 3 O) n －SiR 4 R 5 R 6 …(a1)
[ in formula (a 1), R 2 ～R 6 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. n is an integer of 0 or 1 or more. R is R 1 Is a hydrogen atom or R 7 -O-C (=o) -a group represented by R 7 Is a hydrogen atom, a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom, or R 8 R 9 R 10 Si-silyl group shown as R 8 、R 9 And R is 10 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom.]
[2] The antifouling paint composition as described in [1], wherein the antifouling paint composition further comprises a monocarboxylic acid compound (E).
[3] The antifouling paint composition as described in [2], wherein the monocarboxylic acid compound (E) is a rosin compound (E1).
[4] The antifouling paint composition according to the above [3], wherein the mass ratio of the rosin (E1) to the sum of the silicone-ester polymer (A) and the acrylic polymer (B) (the sum of the polymer (A) and the polymer (B)/the mass of the rosin (E1)) is 0.7 to 4.
[5] The antifouling paint composition according to any of the above [1] to [4], wherein talc is contained in an amount of 2 to 17% by mass based on the solid content of the antifouling paint composition.
[6] The antifouling paint composition according to any of the above [1] to [5], which is used for repairing a deteriorated coating film of an antifouling coating film.
[7] An antifouling coating film formed from the antifouling paint composition of any of the above [1] to [6 ].
[8] A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film of [7] provided on the surface of the substrate.
[9] The substrate with an antifouling coating film according to the above [8], wherein the substrate is at least 1 selected from the group consisting of ships, structures in water, fishery materials and water supply and drainage pipes.
[10] A method for producing a substrate with an antifouling coating film, comprising the step of coating or impregnating the antifouling paint composition according to any of the above [1] to [6] on a substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an antifouling paint composition containing a silicone polymer and medetomidine, which can form an antifouling paint film excellent in crack resistance, adhesion to a deteriorated paint film, and dynamic antifouling property, can be provided.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The components described in the present specification may be used in 1 or 2 or more types, respectively.
"Polymer" is used in the sense of including homopolymers and copolymers.
"(meth) acrylate" is a generic term for acrylate and methacrylate. The same applies to the use examples of (meth) acrylic acid and the like.
"structural unit derived from XX" means that if XX is denoted A 1 A 2 C＝CA 3 A 4 (C=C is a polymerizable carbon-carbon double bond, A 1 ～A 4 An atom or group bonded to a carbon atom, respectively), for example, a structural unit represented by the following formula.
[ antifouling paint composition ]]
The antifouling paint composition (hereinafter also referred to as "composition (I)") of the present embodiment contains a silicone-based polymer (a), an acrylic-based polymer (B), medetomidine (C), and cuprous oxide (D), which are described below, respectively.
Silicon ester polymer (A)
The silicone ester polymer (a) (hereinafter also referred to as "polymer (a)") has a structural unit (a-1) derived from a polymerizable monomer (a 1) represented by the formula (a 1).
R 1 －CH＝C(CH 3 )－COO－(SiR 2 R 3 O) n －SiR 4 R 5 R 6 …(a1)
Each symbol in the formula (a 1) is described below.
R 2 ～R 6 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. Examples of the organic group include a linear or branched alkyl group, a cycloalkyl group, and an aryl group, each having a hetero atom such as an oxygen atom between bonds of carbon atoms, and from the viewpoint of easily obtaining an excellent antifouling coating film having a good balance between crack resistance and long-term dynamic antifouling property due to moderate hydrolyzability, at least 1 selected from a linear or branched alkyl group having 1 to 8 carbon atoms and a phenyl group is preferable, and a branched alkyl group is more preferable.
Examples of the straight-chain or branched alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and 2-ethylhexyl, and isopropyl is preferred.
n is an integer of 0 or 1 or more, preferably 0. The upper limit value of n may be 50, for example.
R 1 Is a hydrogen atom or R 7 -O-C (=o) -groups, preferably hydrogen atoms。R 7 Is a hydrogen atom, a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom, or R 8 R 9 R 10 Si-silyl group shown. R is R 8 、R 9 And R is 10 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. The organic group having 1 to 20 carbon atoms which may have a heteroatom is specifically exemplified as described above.
The polymerizable monomer (a 1) is preferably a trialkylsilyl methacrylate, an alkyl diarylsilyl methacrylate or an aryl dialkylsilyl methacrylate, more preferably a trialkylsilyl methacrylate. Examples of the trialkylsilyl methacrylate include trimethylsilyl methacrylate, triethylsilyl methacrylate, tripropylsilyl methacrylate, triisopropylsilyl methacrylate, tributylsilyl methacrylate, triisobutylsilyl methacrylate, tri-sec-butylsilyl methacrylate, tri-2-ethylhexyl silyl methacrylate, and butyldiisopropylsilyl methacrylate. Further, as the polymerizable monomer (a 1), a polymerizable monomer having n of 2 or more in the above formula (a 1) such as 1-methacryloxynonamethyltetrasiloxane can be exemplified. Among these, trialkylsilyl methacrylate having a branched alkyl group is preferable, and triisopropylsilyl methacrylate is more preferable, from the viewpoint that an antifouling coating film excellent in a balance of crack resistance and long-term dynamic antifouling property having a proper hydrolysis property can be easily obtained.
The number of the structural units (a-1) may be 1 or 2 or more.
The polymer (A) may further have a structural unit (a-2) derived from another ethylenically unsaturated monomer (hereinafter also referred to as "monomer (a 2)").
Examples of the monomer (a 2) include a polymerizable monomer (a 11) represented by the formula (a 11).
R 1 －CH＝CH－COO－(SiR 2 R 3 O) n －SiR 4 R 5 R 6 …(a11)
In the formula (a 11), R 1 ～R 6 And n is the same as the same symbol in formula (a 1).
Examples of the polymerizable monomer (a 11) include trialkylsilyl acrylate, alkyl diarylsilyl acrylate and aryl dialkylsilyl acrylate. Examples of the trialkylsilyl acrylate include trimethylsilyl acrylate, triethylsilyl acrylate, tripropylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, triisobutylsilyl acrylate, tri-sec-butylsilyl acrylate, tri-2-ethylhexyl silyl acrylate, and butyldiisopropylsilyl acrylate. Further, as the polymerizable monomer (a 11), a polymerizable monomer having n of 2 or more in the above formula (a 11) such as 1-acryloyloxy-nonamethyltetrasiloxane is also exemplified.
From the viewpoint of crack resistance (water resistance) of the antifouling coating film, it is preferable to use the polymerizable monomer (a 1) represented by the formula (a 1) instead of the polymerizable monomer (a 11) represented by the formula (a 11).
Examples of the monomer (a 2) include:
(meth) acrylic acid;
(meth) acrylic esters excluding the polymerizable monomers (a 1) and (a 11), specifically, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3, 5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and the like;
alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate;
aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
Glycol-based (meth) acrylates such as ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, and methoxy-dipropylene glycol (meth) acrylate;
vinyl monomers, specifically, vinyl acetate, isobutyl vinyl ether, styrene, vinyl toluene, (meth) acrylonitrile, vinyl propionate, and vinyl benzoate;
(meth) acrylic acid esters containing a metal ester group, specifically zinc (meth) acrylate, zinc di (meth) acrylate, copper (meth) acrylate, and copper di (meth) acrylate.
Among the monomers (a 2), alkyl (meth) acrylates, alicyclic-containing (meth) acrylates, alkoxyalkyl (meth) acrylates, and glycol-based (meth) acrylates are preferable, and alkyl (meth) acrylates and alkoxyalkyl (meth) acrylates are more preferable.
The number of the structural units (a-2) may be 1 or 2 or more.
The proportion of the structural unit (a-1) in the polymer (a) is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less.
The proportion of the structural unit (a-2) in the polymer (a) is preferably 20 mass% or more, more preferably 25 mass% or more, still more preferably 30 mass% or more, preferably 65 mass% or less, more preferably 60 mass% or less, still more preferably 55 mass% or less.
When the ratio of each structural unit is in the above range, the antifouling coating film formed from the composition (I) has moderate hydrolyzability, and tends to be excellent in antifouling property even after a long period of time. The ratio of each structural unit can be determined by NMR (nuclear magnetic resonance spectroscopy), pyro-GC/MS (thermal cracking gas chromatography mass spectrometry), or the like
The weight average molecular weight (Mw) of the polymer (a) is preferably 3,000 or more, more preferably 10,000 or more, preferably 70,000 or less, more preferably 50,000 or less, from the viewpoint of improving the crack resistance of the antifouling coating film formed from the composition (I). Mw can be determined by Gel Permeation Chromatography (GPC) measurement or the like under the conditions employed in examples described later.
The polymer (A) can be used in an amount of 1 or 2 or more.
Acrylic polymer (B) >, acrylic polymer (A)
The hydrolyzed coating film containing the silicone-based polymer (a) and medetomidine (C) dissolves in water at a constant rate for a certain period of time from the initial stage of impregnation, but the water resistance of the coating film may be lowered by hydrolysis inside the coating film, causing cracks or peeling. In response to this problem, if the specific acrylic polymer (B) is blended into the silicone polymer (a), the dynamic antifouling property of the coating film can be maintained and the crack resistance can be improved.
The acrylic polymer (B) (hereinafter also referred to as "polymer (B)") has a structural unit (B-1) derived from glycidyl (meth) acrylate. The structural unit (b-1) contributes to improvement of dynamic antifouling property of an antifouling coating film formed from the composition (I) and adhesion to a deteriorated coating film.
The number of the structural units (b-1) may be 1 or 2.
The proportion of the structural unit (B-1) in the acrylic polymer (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 15% by mass or less. When the proportion of the structural unit (b-1) is not less than the above lower limit, dynamic antifouling property of the antifouling coating film and adhesion to the deteriorated coating film are high, and when the antifouling coating composition contains a pigment described later, sufficient dispersibility of the pigment can be obtained, so that it is preferable. When the proportion of the structural unit (b-1) is not more than the upper limit, the antifouling property is high, and thus it is preferable. Further, when the proportion of the structural unit (b-1) is within a particularly preferable range, the composition tends to be more excellent in storage stability.
The acrylic polymer (B) preferably further has a structural unit (B-2) derived from an aromatic vinyl compound.
The structural unit (b-2) has a phenyl group as a hydrophobic functional group, which contributes to improvement of crack resistance of an antifouling coating film formed from the composition (I), and also contributes to improvement of coating film hardness, impact resistance and abrasion (polishing). The reason for the improvement in the abrasion performance is still unknown, and it is presumed that the structural unit (b-2) improves the film hardness of the formed antifouling film and can exhibit physical abrasion performance against external forces such as frictional resistance in water.
Examples of the aromatic vinyl compound include styrene compounds such as styrene, methyl styrene, 2, 4-dimethyl styrene, ethyl styrene, p-t-butyl styrene, and monochlorostyrene, and among these, styrene is preferable.
The number of the structural units (b-2) may be 1 or 2 or more.
The proportion of the structural unit (B-2) in the acrylic polymer (B) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less. When the proportion of the structural unit (b-2) is not less than the above lower limit, the anti-fouling coating film is preferably high in crack resistance and impact resistance. When the proportion of the structural unit (b-2) is not more than the above upper limit, the antifouling coating film has excellent antifouling properties because the hydrophobicity is not excessively high and the hydrolysis of the polymer (a) is not hindered.
The acrylic polymer (B) further has a structural unit (B-3) derived from another ethylenically unsaturated monomer (hereinafter also referred to as "monomer (B3)").
Examples of the monomer (b 3) include:
(meth) acrylic acid;
(meth) acrylic esters (excluding glycidyl (meth) acrylate), specifically, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3, 5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and the like;
Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate;
aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
Glycol-based (meth) acrylates such as ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, and methoxy-dipropylene glycol (meth) acrylate;
Epoxy group-containing (meth) acrylates other than glycidyl (meth) acrylate;
polyfunctional (meth) acrylates, specifically, tetraethyleneglycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethyleneglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate;
vinyl monomers (excluding aromatic vinyl compounds), specifically, vinyl acetate, isobutyl vinyl ether, vinyl toluene, (meth) acrylonitrile, vinyl propionate, and vinyl benzoate.
Among these, (meth) acrylic esters are preferable, alkyl (meth) acrylates are more preferable, and methyl (meth) acrylate and butyl (meth) acrylate are further preferable.
The number of the structural units (b-3) may be 1 or 2 or more.
By changing the type or amount of the structural unit (B-3), the viscosity and glass transition temperature of the acrylic polymer (B), the hardness of the antifouling coating film, and the like can be adjusted.
The proportion of the structural unit (B-3) in the acrylic polymer (B) is preferably 89% by mass or less, more preferably 82% by mass or less, and still more preferably 75% by mass or less.
The ratio of each structural unit can be determined by the same method as in the silicone-based polymer (a).
The weight average molecular weight (Mw) of the acrylic polymer (B) is preferably 2,000 or more, more preferably 5,000 or more, preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of improving the crack resistance of an antifouling coating film formed from the composition (I). Mw can be determined by Gel Permeation Chromatography (GPC) measurement or the like under the conditions employed in examples described later.
The acrylic polymer (B) may be used in an amount of 1 or 2 or more.
The content of the acrylic polymer (B) in the composition (I) is preferably 5 parts by mass or more relative to 100 parts by mass of the silicone polymer (a), more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 200 parts by mass or less, from the viewpoint of further improving the crack resistance of the antifouling coating film and the adhesion to the deteriorated coating film, and more preferably 130 parts by mass or less, still more preferably 110 parts by mass or less, from the viewpoint of further improving the dynamic antifouling property of the antifouling coating film.
The total content of the silicone-ester polymer (a) and the acrylic polymer (B) is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 30 mass% or less, and still more preferably 25 mass% or less, based on 100 mass% of the total solid content of the composition (I). When the total content is within this range, an antifouling coating film excellent in crack resistance can be easily obtained.
The content of the solid component in the composition (I) is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.
In the present specification, the solid content and the content of the composition (I) are the heating residue (non-volatile component) and the content thereof obtained by the following method or the equivalent method. The composition (I) was measured in a metal test dish of known mass and spread uniformly on the bottom surface. The mixture was heated in a hot air dryer at a temperature of 105 to 110℃for 3 hours to remove volatile components. After taking out and cooling to room temperature (for example: 23 ℃ C.), the mass of the obtained nonvolatile component (heated residual component) was weighed again, and the content of the solid component (heated residual component) was calculated by the following formula.
Content (%) of solid component (heated residual component) =mass (g) of heated residual component (g) ×100/measured composition (I)
The solid content and the content ratio of each component were obtained in the same manner.
Process for producing polymer
The method for producing the polymer (a) and the polymer (B) is not particularly limited, and examples thereof include solution polymerization, suspension polymerization, and pressure polymerization, and solution polymerization using a normal organic solvent under normal pressure is preferable from the viewpoint of high versatility. The solution polymerization may be produced by the following steps.
A reaction vessel having a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet pipe and a heating/cooling jacket was charged with a solvent, and the mixture was heated and stirred under a nitrogen gas stream at a temperature of about 60 to 200 ℃. The polymer (a) or the polymer (B) can be obtained by dropping a mixture of the monomers, the polymerization initiator, and if necessary, a solvent, a chain transfer agent, and the like from a dropping device at the temperature so as to be preferably the ratio of the structural units.
The polymerization initiator is not particularly limited, and various radical polymerization initiators can be used. Specifically, 2 '-azobis (isobutyronitrile), 2' -azobis (2-methylbutyronitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), 4' -azobis-4-cyanovaleric acid, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, t-butyl peroxyoctoate, t-butyl peroxybenzoate, potassium persulfate, sodium persulfate, and the like can be cited. Further, 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 at both the start of the reaction and during the reaction.
The amount of the polymerization initiator used in the production of the polymer (a) or the polymer (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of the monomers (reaction raw materials).
Examples of the solvent that can be used for producing the polymer (a) or the polymer (B) include an organic solvent and water. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, mesitylene, and coal tar naphtha; alcohol solvents such as ethanol, propanol, isopropanol, butanol, and isobutanol; ether solvents such as propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate.
The chain transfer agent is not particularly limited, and examples thereof include α -methylstyrene dimer, thioglycollic acid, diterpene, terpinene, and γ -terpinene; mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform and the like; secondary alcohols such as isopropyl alcohol and glycerin.
When the chain transfer agent is used in the production of the silicone-ester polymer (a), the amount of the chain transfer agent used is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total of the monomers (reaction raw materials).
< medetomidine (C) >)
Medetomidine (C) is a compound represented by the following formula (C1) (+/-) -4- [1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole, has an optical isomer, and may be either one or a mixture of any ratio.
The composition (I) may be an adduct of an imidazole salt, a metal, or the like as part or all of medetomidine. In this case, as a raw material for preparing the composition (I), an adduct of an imidazole salt, a metal or the like may be used, or an adduct of an imidazole salt, a metal or the like may be formed in the composition (I) or an antifouling coating film formed from the composition (I).
Conventional antifouling paint compositions containing no acrylic polymer have insufficient adhesion to a deteriorated film of an antifouling film such as a rosin-containing zinc acrylate resin-based antifouling film, and are difficult to directly coat. In response to this problem, the composition (I) can significantly improve the adhesion to the deteriorated coating film while maintaining the dynamic antifouling property. In addition, if the antifouling paint composition for repair is directly applied to the deteriorated coating film, the surface roughness of the formed antifouling coating film tends to be high due to the surface roughness of the deteriorated coating film, and the fouling tends to physically adhere to the surface of the formed antifouling coating film. The composition (I) can form an antifouling coating film excellent in antifouling property even when it is directly applied to the deteriorated coating film as described above, because it contains medetomidine (C). That is, the composition (I) is suitable for repair coating and repair application to a deteriorated coating film. Here, the deteriorated coating film means a coating film (coating film after use) which is immersed in seawater or fresh water for a certain period of time (for example, 30 weeks or more, preferably 50 weeks or more).
Examples of the antifouling coating film (deteriorated coating film) to be repaired include zinc acrylate resin-based antifouling coating films and silyl resin-based antifouling coating films, and particularly rosin-containing antifouling coating films are preferable, and rosin-containing zinc acrylate resin-based antifouling coating films are more preferable because the problem of adhesion can be solved more favorably.
The rosin-containing antifouling coating film is an antifouling coating film which usually contains 0.5 to 40% by mass of rosin, and is preferably 1 to 30% by mass, more preferably 1.5 to 15% by mass, from the viewpoint of further achieving the effect of the present invention. The antifouling coating film is formed, for example, from an antifouling coating composition containing usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 1.5 to 15% by mass of rosin based on 100% by mass of the solid content of the composition. Specific examples of the rosin include rosin (E1) described below.
The content of medetomidine (C) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 2 mass% or less, still more preferably 1 mass% or less, still more preferably 0.5 mass% or less, and particularly preferably 0.15 mass% or less, based on 100 mass% of the solid content of composition (I). The content of medetomidine (C) in the composition (I) is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the total of the silicone polymer (a) and the acrylic polymer (B). When the content of medetomidine (C) is within this range, the fouling-resistant coating film formed from the composition (I) exhibits more excellent fouling resistance. Further, by making the content of medetomidine (C) in a particularly preferred range, the composition (I) exhibits more excellent storage stability.
< cuprous oxide (D) >)
An antifouling paint composition containing a silicone polymer (a) and medetomidine (C) can improve dynamic antifouling properties against plant species aquatic organisms such as mucus, algae typified by ulva (sea lettuce) and the like by containing cuprous oxide (D).
The content of the cuprous oxide (D) is more than 0 mass% and not more than 55 mass%, preferably 10 to 53 mass%, more preferably 20 to 52 mass% in the solid content of the antifouling paint composition. When the content of cuprous oxide (D) is not less than the above-mentioned lower limit, the dynamic antifouling property of the formed antifouling coating film is improved, and when the content is not more than the above-mentioned upper limit, the composition (I) is excellent in long-term storage stability, and the dynamic antifouling property of the formed antifouling coating film is improved.
The mechanism of action for exerting the above-mentioned effects is not clear, and it is presumed that, for example, an antifouling paint composition containing a silicone-based polymer (a), medetomidine (C) and more than a specific amount of cuprous oxide (D) is remarkable in terms of the increase in molecular weight of the silicone-based polymer (a) and the increase in viscosity of the paint composition due to the interaction of these components, whereas in the antifouling paint composition (I) of the present invention, the increase in viscosity is suppressed and the long-term storage stability is improved because the amount of cuprous oxide (D) is not more than a specific amount. In addition, the mechanism of action is also not clear, and it is presumed that the antifouling paint composition (I) containing the silicone polymer (a) and the polymer (B) and containing the cuprous oxide (D) in a specific amount or less has a moderate increase in the consumption rate of the coating film due to the interaction of these components, and has improved dynamic antifouling properties against aquatic organisms of plant species.
The cuprous oxide (D) preferably has an average particle diameter of about 1 to 30 μm, and more preferably contains 2 to 10 μm from the viewpoint of improving the antifouling property and water resistance of the formed antifouling coating film.
The cuprous oxide (D) is preferably surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, or the like, from the viewpoint of long-term stability of the composition (I) during storage.
As such cuprous oxide (D), commercially available products can be used, and examples thereof include NC-301 (average particle size: 2 to 4 μm) manufactured by NC TECH Co., ltd., NC-803 (average particle size: 6 to 10 μm), red Copp97 NPreturn manufactured by AMERICAN CHEMET Co., purple Copp, loTint97, etc
< monocarboxylic acid Compound (E) >)
The composition (I) preferably contains the monocarboxylic acid compound (E) from the viewpoint of not only improving the antifouling property but also adjusting the consumption rate of the coating film.
Examples of the monocarboxylic acid compound (E) include aliphatic or alicyclic monocarboxylic acids, monocarboxylic acid derivatives thereof, and metal salts thereof. Examples of the monocarboxylic acid derivative include esters and amides of monocarboxylic acids. Examples of the metal salt include zinc salts, copper salts, aluminum salts, magnesium salts, calcium salts, and barium salts. Specific examples of monocarboxylic acids include rosins (E1), naphthenic acids, cycloalkenyl carboxylic acids, bicycloalkenyl carboxylic acids, trimethylisobutenyl cyclohexene carboxylic acids, isononanoic acids, neodecanoic acids, tertiary carboxylic acids (Versatic acids), stearic acid, hydroxystearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, pimaric acid, abietic acid, and neoabietic acid. Among these, rosin (E1) is preferable from the viewpoint that a coating film excellent in crack resistance and long-term antifouling property can be easily obtained.
Examples of the rosin (E1) include rosin such as gum rosin, wood rosin, and tall oil rosin; rosin derivatives such as hydrogenated rosin, disproportionated rosin, and rosin metal salt, and pine tar.
The monocarboxylic acid compound (E) may be used in an amount of 1 or 2 or more.
The mass ratio of the monocarboxylic acid compound (E) to the sum of the silicone-based polymer (A) and the acrylic-based polymer (B) (the sum of the mass of the polymer (A) and the mass of the polymer (B)/the mass of the monocarboxylic acid compound (E)) in the composition (I) is preferably 0.5 or more, more preferably 0.7 or more, preferably 5 or less, and still more preferably 4 or less.
In particular, the mass ratio of the rosin (E1) to the sum of the silicone-ester polymer (a) and the acrylic polymer (B) (the sum of the polymer (a) and the polymer (B)/the mass of the rosin (E1)) in the composition (I) is preferably 0.7 to 4, more preferably 0.7 to 3.5, and still more preferably 0.7 to 3. In one embodiment, the mass ratio exceeds 1.5 and is 3.5 or less. In such a case, the antifouling coating film formed from the composition (I) tends to be more excellent in adhesion to a deteriorated coating film such as a rosin-based antifouling coating film, dynamic antifouling property and crack resistance.
That is, when the mass ratio is 4 or less, adhesion to a deteriorated coating film and dynamic antifouling property tend to be more excellent than when it exceeds 4, and when the mass ratio is 0.7 or more, adhesion to a deteriorated coating film and crack resistance tend to be more excellent than when it is less than 0.7. Therefore, the composition (I) satisfying the above-mentioned condition of the mass ratio can directly coat the deteriorated coating film without using, for example, a binder or the like, and is particularly suitable for repair coating and repair application of the deteriorated coating film.
< other Components >)
The composition (I) may further contain, as other components of the above components, copper and/or copper compounds, organic antifouling agents other than medetomidine (C), colorants, extender pigments, thixotropic agents, dehydrating agents, plasticizers, resins other than the polymer (a) and the polymer (B), and at least 1 kind of solvents.
The components described below may be used in 1 or 2 or more types, respectively.
Copper and/or copper Compound
The composition (I) preferably contains copper and/or a copper compound as an antifouling agent from the viewpoint of further improving antifouling properties against aquatic organisms of animal species. Copper may be, for example, copper powder. Examples of the copper compound include copper thiocyanate and copper-nickel alloy, and copper thiocyanate is preferable. Copper (D) oxide is not classified as the copper compound, and copper pyrithione is not a copper compound but is classified as the following organic antifouling agent.
The content of copper and/or copper compound is preferably 0.1 to 45% by mass, more preferably 1 to 35% by mass, relative to 100% by mass of the total solid content of the composition (I).
Organic antifouling Agents
The composition (I) preferably contains an organic antifouling agent other than medetomidine (C) as an antifouling agent. The organic antifouling agent is a component for further improving the antifouling property of the antifouling coating film.
Examples of the organic stain-proofing agent include copper pyrithione, zinc pyrithione and other metal pyrithione, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, triphenylborane pyridine, 4-isopropyldipyridyl diphenylmethylborane, N-dimethyl-N '- (3, 4-dichlorophenyl) urea, N- (2, 4, 6-trichlorophenyl) maleimide, 2-methylthio-4-t-butylamino-6-cyclopropylamino-1, 3, 5-triazine, 2,4,5, 6-tetrachloro-m-phenylenediamine, dimethyldithiocarbamate zinc ethylene dithiocarbamate, chloromethyl N-octyldisulfide, N' -dimethyl-N-phenyl- (N-fluorodimethylthio) sulfonamide, N '-dimethyl-N-methylphenyl- (N-fluorothio) sulfonamide, tetramethyl-2, 6' -dichloro-4-dimethylamino-6-cyclopropylamino-1, 3, 5-triazine, 2,4,5, 6-tetramethyl-thiocarbamate, zinc-bis- (2-fluoro-methylsulfide) sulfide, and zinc-bis- (2, 6-dichloro-methylphenyl) sulfide. Among these, copper pyrithione, zinc pyrithione and other metal pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, zinc bis (dimethyldithiocarbamate) ethylene dithiocarbamate are preferable, and copper pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one are more preferable.
The content of the organic antifouling agent other than medetomidine (C) is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, relative to 100% by mass of the total solid content of the composition (I).
Colorant(s)
As the colorant, various pigments and dyes of conventionally known organic and inorganic systems can be used. Examples of the organic pigment include naphthol red and phthalocyanine blue. Examples of the inorganic pigment include carbon black, iron oxide red, barite powder, titanium white (titanium oxide), and iron oxide yellow. The composition (I) contains a colorant, and is preferable in that the hue of an antifouling coating film obtained from the composition can be arbitrarily adjusted.
The content of the colorant is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, relative to 100% by mass of the total solid content of the composition (I).
Extender pigment
Examples of extender pigments include zinc oxide, talc, silica, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon black, aluminum hydroxide, magnesium carbonate, barium sulfate, and zinc sulfide. Among these, zinc oxide, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar are preferable.
The composition (I) preferably contains an extender pigment, and more preferably contains talc, from the viewpoint of improving the physical properties of the coating film such as crack resistance of the resulting antifouling coating film.
The content of the extender pigment is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, relative to 100% by mass of the total solid content of the composition (I).
The content of talc is preferably 2 to 17% by mass relative to 100% by mass of the total solid content of the composition (I) from the viewpoint of further improving the physical properties of the coating film such as crack resistance.
Thixotropic agent
Thixotropic agents are ingredients that contribute to sag and sedimentation resistance of the coating.
Examples of thixotropic agents (anti-sagging agents, anti-settling agents) include salts selected from the group consisting of organic bentonite, amine salts of Al, ca or Zn, stearates, lecithin salts and alkyl sulfonates; waxes selected from polyethylene waxes, oxidized polyethylene waxes, amide waxes, hydrogenated castor oil waxes, and polyamide waxes; synthesizing the micro-powder silicon dioxide.
The thixotropic agent is used for improving the anti-precipitation property of solid materials such as copper and/or copper compounds, organic anti-fouling agents, colorants, extender pigments, dehydrating agents and the like during storage of the anti-fouling coating composition and the coating operability during coating.
The content of the thixotropic agent is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, relative to 100% by mass of the total solid content of the composition (I).
Dehydrating agents
Examples of the dehydrating agent include inorganic dehydrating agents and organic dehydrating agents, for example, inorganic dehydrating agents include synthetic zeolite, anhydrite and hemihydrate gypsum, and examples of the organic dehydrating agents include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane, and alkyl orthoformates such as polyalkoxysilanes, methyl orthoformate and ethyl orthoformate, which are condensates thereof. The dehydrating agent is used for preventing gelation caused by decomposition of the hydrolyzable resin due to moisture generated during production and/or storage of the antifouling paint composition.
The content of the dehydrating agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to 100% by mass of the total solid content of the composition (I).
Plasticizer(s)
Examples of the plasticizer include normal paraffins, chlorinated paraffins, petroleum resins, ketone resins, tricresyl phosphate, polyvinyl ethyl ether, and dialkyl phthalates, and among these, chlorinated paraffins, petroleum resins, and ketone resins are preferable. The composition (I) contains a plasticizer, and is preferable in view of further improving the crack resistance and water resistance of an antifouling coating film obtained from the composition.
The chlorinated paraffin may have any of linear and branched molecular structures, and may be liquid or solid (powder) at room temperature.
The average number of carbon atoms of the chlorinated paraffin is preferably 8 to 30, more preferably 10 to 26, in 1 molecule. The antifouling paint composition containing the chlorinated paraffin can form an antifouling coating film with less cracks and peeling. Further, when the average carbon number is 8 or more, the effect of suppressing the occurrence of cracks is high, and when the average carbon number is 30 or less, the antifouling property is not suppressed, so that it is preferable.
The chlorinated paraffin preferably has a viscosity (unit POISE, measurement temperature 25 ℃) of 1 or more, more preferably 1.2 or more, and a specific gravity (25 ℃) of 1.05 to 1.80g/cm 3 More preferably 1.10 to 1.70g/cm 3 。
Examples of the petroleum resin include C5-based, C9-based, styrene-based, dicyclopentadiene-based petroleum resins and hydrogenated products thereof.
The content of the plasticizer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to 100% by mass of the total solid content of the composition (I).
Resins other than Polymer (A) and Polymer (B)
The composition (I) may contain resins other than the polymer (A) and the polymer (B). Examples of the resins include water-insoluble or poorly water-soluble resins such as polyester resins, unsaturated polyester resins, fluororesins, polybutene resins, polyurethane resins, epoxy resins, polyamide resins, vinyl resins (vinyl chloride copolymers, ethylene-vinyl acetate copolymers, etc.), styrene-butadiene copolymer resins, alkyd resins, coumarone resins, terpene phenol resins, silicone rubbers, and chlorinated rubbers.
The resin content is, for example, 0.01 to 100 parts by mass based on 100 parts by mass of the total of the polymer (A) and the polymer (B).
Solvent (S)
In the composition (I), a solvent such as water or an organic solvent may be contained as needed in order to improve dispersibility of each component or to adjust viscosity of the composition. The solvent may be a solvent used in preparing the polymer (A) or the polymer (B), or may be a solvent which is additionally added in preparing the antifouling paint composition by mixing the polymer (A) and the polymer (B) with other components as required. As the solvent, an organic solvent is preferable. The organic solvent may be the organic solvent described in the item < method for producing a polymer >.
When the composition (I) contains a solvent, the content thereof is determined in a preferable amount according to the desired viscosity corresponding to the coating form of the coating composition. The content of the solvent in the composition (I) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the content of the solvent is too large, problems such as a decrease in sagging resistance may occur.
Process for producing antifouling coating composition
The composition (I) can be suitably produced by a known method, except that the polymer (a), the polymer (B), the medetomidine (C) and the specific amount of cuprous oxide (D) are used. For example, the polymer (a), the polymer (B), the medetomidine (C), and the specific amount of cuprous oxide (D), and if necessary, the monocarboxylic acid compound (E) and/or the other components mentioned above may be added to a stirring vessel at one time or in any order, and the components may be mixed by a known stirring and mixing method, and dispersed or dissolved in a solvent to prepare the aqueous dispersion.
Examples of the stirring and mixing method include a method using a paint shaker, a high-speed disperser, a sand mill, a basket mill, a ball mill, a three-roll mill, a Ross mixer, a planetary mixer, and a pin-and-socket type universal mixer.
[ use of antifouling paint composition ]]
The antifouling coating film (hereinafter also referred to as "antifouling coating film (J)") of the present embodiment is formed from the composition (I). The substrate with an antifouling coating film (hereinafter also referred to as "antifouling substrate (K)") of the present embodiment includes a substrate and an antifouling coating film (J) provided on the surface of the substrate.
The method for producing the antifouling substrate (K) comprises a step of coating or impregnating a substrate (object or coated object) with the composition (I), and a step of drying a coated body or impregnated body obtained by coating or impregnating the substrate when the composition (I) contains a solvent.
For example, a known method such as air spraying, airless spraying, brushing, and roller can be used for the application.
The composition (I) coated or impregnated by the above method is dried, for example, by leaving it at-5 to 30℃for about 1 to 14 days, more preferably about 1 to 7 days, and still more preferably about 1 to 5 days, whereby an antifouling coating film (J) can be obtained. In addition, the drying of the composition (I) may be performed while blowing under heating.
Alternatively, the antifouling substrate (K) can be produced by forming an antifouling coating film (J) from the composition (I) on the surface of a temporary substrate, and peeling the antifouling coating film (J) from the temporary substrate to attach the antifouling coating film (J) to the substrate to be antifouling. In this case, the antifouling coating film (J) may be attached to the substrate via the adhesive layer.
The substrate may be primed on its surface, or may have a layer formed of various resin-based coatings such as an epoxy-based coating, a vinyl-based coating, an acrylic-based coating, and a urethane-based coating on its surface. The substrate may be an antifouling substrate having an antifouling coating film, for example, an antifouling substrate having a deteriorated antifouling coating film such as a rosin-containing zinc acrylate-based antifouling coating film. The surface of the substrate on which the antifouling coating film (J) is provided in this case means the surface after plasma treatment, the surface of the layer formed of the above-mentioned coating material, and the surface of the antifouling coating film.
The substrate is not particularly limited, and the composition (I) is preferably used for long-term antifouling of a substrate in a wide industrial field such as ships, fisheries, underwater structures, and the like. Thus, examples of the base material include ship hulls such as large steel ships including container ships and tankers, fishing ships, FRP (glass fiber reinforced plastic) ships, wooden ships, and yachts, new or repaired ships including those, underwater structures such as oil pipelines, water pipelines, circulating pipes, factories and power plants, water supply and drainage ports of nuclear power plants, submarine cables, machines utilizing seawater (sea water pumps and the like), ultra-large floating body type marine constructions, structures for civil engineering in water such as coastal roads, submarine tunnels, harbor facilities, canals and waterways, and the like, fishery materials such as supply and drainage pipes for seawater such as ropes, fishing nets, fishing gear, floats, buoys, factories and power plants, underwater water supply and drainage pipes for spectacles, oxygen cylinders, swimwear, fish, and the like. Of these, vessels, underwater structures, fishery materials, and water supply and drainage pipes are preferable, vessels and underwater structures are more preferable, and vessels are particularly preferable.
When the antifouling substrate (K) is produced, the composition (I) may be directly applied to the surface of the substrate when the substrate is a fishing net or a steel sheet, or the surface of the substrate may be impregnated with the composition (I) when the substrate is a fishing net, or the surface of the substrate may be coated with a base material such as an anticorrosive agent or a primer to form a base layer when the substrate is a steel sheet, and then the composition (I) may be applied to the surface of the base layer. In addition, as in a steel sheet having a deteriorated anti-fouling coating film (for example, a deteriorated coating film of a rosin-containing zinc acrylate resin-based anti-fouling coating film), the anti-fouling coating film (J) may be formed on the surface of a substrate on which the anti-fouling coating film (J) or a conventional anti-fouling coating film (for example, a deteriorated coating film of a rosin-containing zinc acrylate resin-based anti-fouling coating film) is formed for the purpose of repairing.
The thickness of the antifouling coating film (J) is not particularly limited, and is, for example, about 30 to 1000. Mu.m. In addition, when the composition (I) is applied to a substrate to form an antifouling coating film (J), the thickness of the antifouling coating film (J) formed by 1-time coating (when the composition (I) contains a solvent, the thickness of the coating film after removal of the solvent) is preferably 10 to 300. Mu.m, more preferably 30 to 200. Mu.m, and the thickness is applied in 1 to more times.
The ship having the antifouling coating film (J) can prevent the adhesion of aquatic organisms, thereby preventing the reduction of the ship speed and the increase of the burnup caused by the adhesion. The underwater structure having the antifouling coating film (J) can prevent the adhesion of aquatic organisms for a long period of time, and can maintain the function of the underwater structure for a long period of time. The fishing net with the antifouling coating film (J) can prevent the adhesion of aquatic organisms, thereby preventing the clogging of the net. In addition, the water supply and drainage pipe having the antifouling coating film (J) on the inner surface can prevent the adhesion and propagation of aquatic organisms, thereby preventing the blockage of the water supply and drainage pipe and the reduction of the flow rate.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited to the examples. In the following examples and comparative examples, "parts" means "parts by mass".
[ measurement conditions ]]
The polymer was subjected to Gel Permeation Chromatography (GPC) measurement, and the polymer solution was subjected to measurement of the content of the heating residual component. The measurement conditions are as follows.
< GPC measurement conditions >
The device comprises: "HLC-8320GPC" (manufactured by Tosoh Co., ltd.)
Column: "TSKgel guardcolumn SuperMP (HZ) -M+ TSKgel SuperMultiporeHZ-M+ TSKgel SuperMultiporeHZ-M" (all of them are manufactured by Tosoh Co., ltd.)
Eluent: tetrahydrofuran (THF)
Flow rate: 0.35ml/min
A detector: RI (RI)
Chromatographic column oven temperature: 40 DEG C
Standard curve: standard polystyrene and styrene monomer
Sample preparation method: THF was added to the polymer solutions obtained in the respective production examples, and the polymer solutions were diluted, and then filtered through a membrane filter, whereby the obtained filtrates were used as GPC measurement samples.
< conditions for measuring the content of solid component (heating residual component >)
The polymer solution was measured in a metal test dish of a known mass, uniformly spread on the bottom surface, and heated in a hot air dryer at a temperature of 105 to 110℃for 3 hours to remove volatile components. After taking out and cooling to room temperature (for example, 23 ℃ C.), the mass of the obtained nonvolatile component (heated residual component) was weighed, and the content of the solid component was calculated by the following formula.
Content (%) of solid component (heated residual component) =mass (g) of heated residual component (g) ×100/measured polymer solution
[ production example of Polymer ]]
Production example 1]Preparation of solution of Silicone ester Polymer (A)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet tube and a dropping device was charged with 43 parts of xylene and 10 parts of triisopropylsilyl methacrylate, and the mixture was heated and stirred under a nitrogen atmosphere so that the liquid temperature became 80 ℃. A mixture of monomers (50 parts of triisopropylsilyl methacrylate, 25 parts of 2-methoxyethyl methacrylate, 10 parts of methyl methacrylate, 5 parts of n-butyl acrylate) and a polymerization initiator (1.35 parts of 2,2' -azobis (isobutyronitrile)) was dropwise added from a dropwise adding device to the reaction vessel over 2 hours while maintaining the temperature. Then, the temperature of the liquid was raised to 95℃after stirring at the same temperature for 1 hour and stirring at 88℃for 1 hour. After maintaining the temperature and adding 0.1 part of 2,2' -azobis (isobutyronitrile) dropwise every 30 minutes in total 4 times, the liquid temperature was raised to 105 ℃. After stirring at this temperature for 30 minutes with heating, 23.7 parts of xylene was added to the reaction vessel to obtain a solution of the silicone ester polymer (A-1).
The same procedure as described above was conducted except that the monomers were changed as shown in Table 1, to obtain a solution of the silicone-ester polymer (A-2) and a solution of the silicone-ester polymer (cA-1) for comparison.
Production example 2]Production of a solution of acrylic Polymer (B)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet tube and a dropping device was charged with 66.7 parts of xylene, and the mixture was heated and stirred under a nitrogen atmosphere so that the liquid temperature became 110 ℃. A mixture of monomers (50 parts of styrene, 15 parts of methyl methacrylate, 25 parts of n-butyl acrylate, 10 parts of glycidyl methacrylate) and a polymerization initiator (1.5 parts of 2,2' -azobis (isobutyronitrile), 1 part of t-butyl peroxybenzoate) was dropwise added to the reaction vessel from the dropwise adding apparatus over 3 hours under the same conditions, and heated and stirred at the same temperature for 1 hour, and heated and stirred at 120℃for 1 hour, and then heated and stirred at 130℃for 1 hour, and 7.16 parts of xylene was added to the reaction vessel to obtain a solution of the acrylic polymer (B-1).
The same operations as described above were performed except that the monomers were changed as shown in Table 2, to obtain solutions of acrylic polymers (B-2) to (B-4) and solutions of acrylic polymers (cB-1) to (cB-2) for comparison.
The weight average molecular weights of these silicone-based polymer and acrylic-based polymer and the content of the solid component (heating residual component) of these solutions are shown in tables 1 and 2. The numerical value of the monomer represents the amount (parts by mass)
TABLE 1
TABLE 2
[ preparation of antifouling paint composition ]]
Example 1]
An antifouling paint composition was prepared as follows.
To a polyethylene container were added 0.1 part of medetomidine (Selektope (registered trademark)) and 0.9 part of methoxypropanol (PGM), and the mixture was mixed using a paint shaker until the medetomidine was uniformly dissolved. To the resulting solution, 14.0 parts of xylene and 6.5 parts of gum rosin (chinese gum rosin WW) were added, and the mixture was mixed again using a paint shaker until the rosin was uniformly dissolved. Thereafter, 12.0 parts of a solution of the silicone polymer (A-1) and 5.0 parts of a solution of the acrylic polymer (B-1) were added to the obtained solution and stirred until they were uniformly mixed, followed by further adding 10 parts of zinc oxide (No. 3 zinc oxide), 37 parts of cuprous oxide (NC-301), 2.0 parts of titanium oxide (TIPAQUE R-930), 1.5 parts of iron oxide red (TODA COLOR NM-50), 6.0 parts of talc (FC-1), 1.0 parts of copper pyrithione (Copper Omadine Powder), 2.0 parts of polyethylene oxide wax (DISPARON 4200-20X) and 0.5 parts of tetraethoxysilane (Ethyl silicate 28), and further adding 200 parts of glass beads and stirring them for 1 hour using a paint shaker to disperse them. To the resulting dispersion was added 1.5 parts of an amide wax (disporon a 630-20X), and after stirring for 20 minutes using a paint shaker, glass beads were removed from the mixture using a 80-mesh filter screen, to obtain an antifouling paint composition.
Examples 2 to 19 and comparative examples 1 to 7]
An antifouling paint composition was prepared in the same manner as in example 1 except that the types and the amounts of the components were changed as shown in table 3.
[ antifouling ]Evaluation of physical Properties of coating composition]
The physical properties of the coating films formed using the antifouling coating compositions obtained in examples and comparative examples were evaluated as follows. The results obtained are shown in Table 3.
< crack resistance >)
An epoxy anticorrosive paint (trade name "Bannoh 500", manufactured by China paint Co., ltd., hereinafter referred to as "epoxy 1") was applied to a sandblasted steel plate having a size of 300mm in length, 100mm in width and 2.3mm in thickness by air spraying so as to have a thickness of 150 μm in terms of a dry film, and dried at 23℃for 1 week to form a cured coating film. Then, an epoxy-based adhesive paint (trade name "Bannoh 500N", manufactured by China paint Co., ltd., hereinafter referred to as "epoxy 2") was applied to the cured coating film of epoxy 1 by air spraying so that the dry film thickness became 100. Mu.m, and the film was dried at 23℃for 24 hours.
Next, each of the compositions prepared in examples and comparative examples was applied to the surface of the cured coating film of the epoxy 2 to a dry film thickness of 200 μm, and then dried at 23 ℃ for 7 days to form an antifouling coating film, thereby producing a crack resistance test board.
The crack resistance test plate thus produced was immersed in natural seawater heated to 50℃for 6 months, and the presence or absence of cracks (area basis) was confirmed.
Evaluation criterion (evaluation based on the ratio of the area of crack to the total area of the surface of the coating film, qualification of 4 or more.)
5: no cracks were confirmed.
4: cracks were confirmed in the portion below 2%.
3: cracks were confirmed at a portion of 2% or more and less than 30%.
2: cracks were confirmed at 30% or more and less than 80%.
1: cracks were confirmed in 80% or more.
< adhesion to deteriorated coating film >
Blast-treated steel sheet having dimensions of 300mm in length, 100mm in width and 3.2mm in thickness was used to resist crackingIn the same procedure, epoxy 1 was coated to a dry film thickness of 150 μm and epoxy 2 was coated to a dry film thickness of 100. Mu.m. A zinc acrylate-based antifouling paint 1 containing rosin (rosin content: 6 mass% relative to 100 mass% of the solid content of the antifouling paint) was applied to the surface of a cured coating film formed of epoxy 2 so that the dry film thickness was 200 μm, and dried at 23 ℃ for 7 days. The panels were immersed in seawater for 1 year with a test raft. The plate was lifted up at 80kgf/cm 2 Is subjected to water washing under pressure. After drying, the antifouling paint composition prepared in the example or comparative example was applied to the surface of the deteriorated coating film 1 formed from the zinc acrylate-based antifouling paint 1 so that the dry film thickness was 200 μm, and dried at 23℃for 7 days to form an antifouling coating film, and an adhesion test board 1 to the deteriorated coating film 1 was produced. The plate was immersed in natural seawater at 23℃for 10 months and then dried at 23℃for 1 day. Then, 25 checkerboard peeling tests (cross cut method) of 4mm×4mm were carried out basically in accordance with JIS K5600-5-6 (1999), but also in accordance with the dry film thickness, and adhesion was evaluated with respect to the remaining coating film area of the test object area.
Evaluation criterion (more than 4 is qualified)
5: the stripping area is lower than 5%
4: the peeling area is 5% or more and less than 10%
3: the peeling area is more than 10% and less than 40%
2: the peeling area is 40% or more and less than 70%
1: the peeling area is 70% or more and less than 100%
As the deteriorated coating film, a test plate was produced in the same manner as in the zinc acrylate-based antifouling paint 1, using a rosin-free zinc acrylate-based antifouling paint 2, a rosin-containing silyl-based antifouling paint 3 (rosin content: 7 mass% with respect to 100 mass% of the solid content of the antifouling paint 3), and a rosin-containing silyl-based antifouling paint 4 (rosin content: 2 mass% with respect to 100 mass% of the solid content of the antifouling paint 4) instead of the zinc acrylate-based antifouling paint 1. After immersing these test boards in seawater for 1 year, the test rafts were washed with water in the same manner as described above, and the surfaces of the deteriorated coating film 2 formed from the zinc acrylate-based antifouling paint 2, the deteriorated coating film 3 formed from the silyl group-based antifouling paint 3, and the deteriorated coating film 4 formed from the silyl group-based antifouling paint 4 were coated with the antifouling coating composition prepared in examples or comparative examples so that the dry film thickness was 200 μm, and dried at 23℃for 7 days to form antifouling coating films, thereby producing adhesion test boards 2 to 4 to the deteriorated coating films 2 to 4. Then, the plates were immersed in artificial seawater at 40℃for 6 months, and adhesion was evaluated in the same manner as described above.
< dynamic stain resistance >
A dynamic stain resistance test plate was produced in the same procedure as the crack resistance test plate using a blast-treated steel plate having dimensions of 150mm in length, 70mm in width and 1.6mm in thickness. The test plate obtained was immersed in sea water in the sea area of wu city, guangda county, japan, and a water flow was generated so as to be about 15 knots per hour by using a rotary rotor, and the antifouling coating surface of the test plate was washed with the water flow for 12 months, and the ratio of the area to which aquatic organisms were attached to the antifouling coating surface of the test plate was evaluated by visual observation.
Evaluation criterion (more than 4 is qualified)
5: no deposit was observed.
4: adhesion of mucus was confirmed in the portion below 10%.
3: the adhesion of mucus was confirmed in the portion of 10% or more and less than 60%.
2: the adhesion of mucus was confirmed in the portion of 60% or more and less than 90%.
1: adhesion of mucus was confirmed in the portion above 90%.
TABLE 3
[ Table 3 continuation ]
Evaluation of storage stability of antifouling paint composition]
The storage stability of the antifouling paint compositions obtained in examples and comparative examples was evaluated as follows. The results obtained are shown in Table 4.
< storage stability >
The initial viscosity of each of the antifouling paint compositions of examples and comparative examples, which were prepared by the above-described method, was measured after 1 day of preparation, and then stored at 50℃for 2 months. The viscosity of each composition after storage was measured, and the viscosity increase rate obtained by the following formula was calculated. If the viscosity increase rate is less than 20%, the test piece is qualified.
Further, the antifouling paint composition having a viscosity increase rate of 20% or more causes problems such as a significant decrease in paint workability, an increase in the amount of organic solvent used for dilution, and an increase in environmental load.
Viscosity increase rate = (viscosity after storage-initial viscosity)/initial viscosity×100
TABLE 4
/>
Further, details of the components used in examples and comparative examples are as follows.
TABLE 5
/>

Claims (10)

1. An antifouling paint composition comprising:
a silicone-ester polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a 1) represented by the formula (a 1),
An acrylic polymer (B) having a structural unit (B-1) derived from glycidyl (meth) acrylate,
Medetomidine (C), sum
Cuprous oxide (D),
the content of the cuprous oxide (D) in the solid content of the antifouling paint composition exceeds 0 mass% and is 55 mass% or less,
R 1 －CH＝C(CH 3 )－COO－(SiR 2 R 3 O) n －SiR 4 R 5 R 6 …(a1)
in the formula (a 1), R 2 ～R 6 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms and having a heteroatom, n is an integer of 0 or 1 or more, R 1 Is a hydrogen atom or R 7 -O-C (=o) -a group represented by R 7 Is a hydrogen atom, a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom, or R 8 R 9 R 10 Si-silyl group shown as R 8 、R 9 And R is 10 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom.
2. The antifouling coating composition of claim 1 wherein:
also contains a monocarboxylic acid compound (E).
3. An antifouling coating composition according to claim 2, wherein:
the monocarboxylic acid compound (E) is rosin (E1).
4. An antifouling coating composition according to claim 3, wherein:
the mass ratio of the rosin (E1) to the total of the silicone polymer (A) and the acrylic polymer (B), i.e., the total mass of the polymer (A) and the polymer (B), to the mass of the rosin (E1) is 0.7 to 4.
5. The antifouling coating composition of claim 1 wherein:
further comprises talc in an amount of 2 to 17% by mass based on the solid content of the antifouling paint composition.
6. The antifouling coating composition of claim 1 wherein:
it is used for repairing deteriorated coating films of antifouling coating films.
7. An antifouling coating film characterized in that:
formed from the antifouling paint composition as claimed in any of claims 1 to 6.
8. A substrate with an antifouling coating film, characterized by comprising:
Substrate and method for producing the same
The antifouling coating film of claim 7 provided on the surface of the substrate.
9. The substrate with an antifouling coating film as claimed in claim 8, wherein:
the base material is at least 1 selected from ships, structures in water, fishery materials and water supply and drainage pipes.
10. A method for producing a substrate with an antifouling coating film, characterized by comprising:
the method comprising the step of coating or impregnating the substrate with the antifouling paint composition according to any of claims 1 to 6.
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