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WO2020235516A1 - Revêtement antisalissure multicouches et objet revêtu portant ledit revêtement sur une surface - Google Patents

Revêtement antisalissure multicouches et objet revêtu portant ledit revêtement sur une surface Download PDF

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Publication number
WO2020235516A1
WO2020235516A1 PCT/JP2020/019578 JP2020019578W WO2020235516A1 WO 2020235516 A1 WO2020235516 A1 WO 2020235516A1 JP 2020019578 W JP2020019578 W JP 2020019578W WO 2020235516 A1 WO2020235516 A1 WO 2020235516A1
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WIPO (PCT)
Prior art keywords
monomer
copolymer
coating film
mass
antifouling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/019578
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English (en)
Japanese (ja)
Inventor
拓也 安井
崇 松木
英典 和久
慧 小林
基道 伊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Kasei Co Ltd
Original Assignee
Nitto Kasei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Kasei Co Ltd filed Critical Nitto Kasei Co Ltd
Priority to KR1020217041925A priority Critical patent/KR102895008B1/ko
Priority to CN202080037675.7A priority patent/CN113939565A/zh
Publication of WO2020235516A1 publication Critical patent/WO2020235516A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • 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
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
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    • C09D5/1675—Polyorganosiloxane-containing compositions
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    • 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

Definitions

  • the present invention relates to a multi-layer antifouling coating film and a coating material having the coating film on the surface.
  • Aquatic pollutants such as Fujitsubo, Serupura, Murasakiigai, Fusakokemushi, Hoya, Green laver, Sea lettuce, and slime are applied to underwater structures such as ships (especially the bottom of ships), fishing nets, fishing net accessories, and other fishing equipment and power plant water pipes. Adhesion causes problems such as impairing the functions of those ships and impairing their appearance.
  • an antifouling paint composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is gradually released from the antifouling coating film to prevent fouling over a long period of time.
  • Patent Document 1 A technique for exerting performance is known (Patent Document 1).
  • the coating film renewability by hydrolysis as in Patent Document 1 has poor coating film renewability at the initial stage of flooding. Especially during the dressing period, since the ship is in a stationary state, the paint film renewability is very poor. Therefore, in the initial stage of flooding, slime or the like easily adheres, and then barnacles, cell plastics, or the like are subsequently adhered, resulting in problems such as deterioration of fuel efficiency and deterioration of appearance.
  • the present invention has been made in view of such circumstances, and provides a multi-layer antifouling coating film having excellent impact resistance and excellent both antifouling property at the initial stage of flooding and long-term antifouling property. is there.
  • the present invention is a multi-layer antifouling coating having a lower layer coating film and an upper layer coating film formed on the lower layer coating film, wherein the upper layer coating film contains a copolymer A, and the lower layer coating film is ,
  • the upper layer coating film and the lower layer coating film each contain an antifouling agent, and the copolymer A contains a monomer (a) and a monomer (c), respectively.
  • the copolymer A is the first monomer.
  • the weight mixture is 100% by mass
  • the content of the monomer (a) is 10 to 45% by mass
  • the content of the monomer (b) is 0 to 15% by mass
  • the simple The content of the weight (c) is 20 to 50% by mass
  • the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass
  • the copolymer B is Is a copolymer other than the copolymer A
  • the total content of the monomer (a) and the monomer (b) is 46, assuming that the second monomer mixture is 100% by mass.
  • a multi-layer antifouling coating having a content of up to 65% by mass is provided.
  • the present inventor has found that the multi-layer antifouling coating film having the above structure can solve the above problems, and has reached the completion of the present invention.
  • the multi-layer antifouling coating film according to the embodiment of the present invention has a lower layer coating film and an upper layer coating film formed on the lower layer coating film. Both the lower layer coating film and the upper layer coating film are hydrolysis type antifouling coating films.
  • the upper coating film contains the copolymer A and an antifouling agent.
  • the upper layer coating film can be formed by using an antifouling coating composition obtained by dissolving or dispersing the components contained in the upper layer coating film in a solvent.
  • Copolymer A is a copolymer of the first monomer mixture.
  • the first monomer mixture contains a monomer (a) and a monomer (c), and may contain a monomer (b), and is a single amount other than the monomers (a) to (c). It may include the body.
  • the copolymer A has a content of the monomer (a) of 10 to 45% by mass and a content of the monomer (b) of 0.
  • the content of the monomer (c) is 20 to 50% by mass, and the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass. %.
  • the content of the monomer (a) is, for example, 10, 15, 20, 25, 30, 35, 40, 45% by mass, and is in the range between any two of the numerical values exemplified here. It may be inside.
  • the content of the monomer (b) is, for example, 0, 5, 10, 15% by mass, and may be in the range between any two of the numerical values exemplified here.
  • the content of the monomer (c) is, for example, 20, 25, 30, 35, 40, 45, 50% by mass, and is within the range between any two of the numerical values exemplified here.
  • the total content of the monomer (a) and the monomer (b) is, for example, 10, 15, 20, 25, 30, 35, 40, 45% by mass, and the numerical values exemplified here. It may be within the range between any two of.
  • the monomer (a) is a triorganosilyl methacrylate monomer represented by the general formula (1).
  • R 1 to R 3 are the same or different branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, respectively.
  • R 1 to R 3 represent branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, which are the same or different from each other.
  • Examples of the branched alkyl group having 3 to 8 carbon atoms include an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, and 1,1.
  • -Dimethylpropyl group 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methylheptyl group, 2-methylbutyl group
  • Examples thereof include a group, a 2-ethylbutyl group, a 2,2-dimethylpropyl group, a cyclohexylmethyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a 3-methylpentyl group and the like.
  • R 1 to R 3 are an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group. Particularly preferred are isopropyl groups.
  • Examples of the monomer (a) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tris-butylsilyl methacrylate, triisopentylsilyl methacrylate, triphenylsilyl methacrylate, diisopropylphenylsilyl methacrylate, and methacrylic acid.
  • Diisopropylisobutylsilylate acid diisopropyls-butylsilylmethacrylate, diisopropylisopentylsilyl methacrylate, isopropyldiisobutylsilylacrylate, isopropyldis-butylsilylmethacrylate, t-butyldiisoputylsilylmethacrylate, t-butyldiisomethacrylate Pentylsilyl, t-butyldiphenylsilyl methacrylate, diisopropyltexylsilyl methacrylate, diisopropylcyclohexylsilyl methacrylate, tricyclohexylsilyl methacrylate, tri-1,1-dimethylpentylsilyl methacrylate, tri 2,2-dimethylpropyl methacrylate
  • Examples thereof include silyl, tricyclohexylmethylsily
  • Preferred examples thereof include triisopropylsilyl methacrylate, tris-butylsilyl methacrylate, t-butyldiphenylsilyl methacrylate, tri2-ethylhexylsilyl methacrylate and the like.
  • These monomers (a) can be used alone or in combination of two or more.
  • the monomer (b) is a triorganosilyl monomeric acid acrylate represented by the general formula (2).
  • R 1 to R 3 are the same or different branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, respectively.
  • R 1 to R 3 of the general formula (2) is the same as the description of R 1 to R 3 of the general formula (1).
  • Examples of the monomer (b) include those in which the name "methacrylic acid” of the compound exemplified as the monomer (a) is changed to "acrylic acid”.
  • the monomer (c) is a (meth) acrylic acid ester monomer represented by the general formula (3).
  • the monomer (c) has an acryloyloxy group or a methacryloyloxy group, and also has an alkoxy or allyloxypolyethylene glycol group.
  • R 4 is a hydrogen atom or a methyl group
  • R 5 is an alkyl group or an aryl group
  • n is 1 to 25.
  • the degree of polymerization (n) of polyethylene glycol is 1 to 25, preferably 1 to 5, and specifically, for example, 1, 2, 3, 4, 5, 10, 15, 20, 25. It may be within the range between any two of the numerical values exemplified in 1.
  • alkyl group examples include a linear or branched alkyl group having 12 or less carbon atoms such as methyl, ethyl, propyl and butyl; a cyclic alkyl group such as cyclohexyl and substituted cyclohexyl.
  • Examples of the aryl group include an aryl group and a substituted aryl.
  • Examples of the substituted aryl group include a halogen, an alkyl group having up to about 18 carbon atoms, an acyl group, an aryl group substituted with a nitro group, an amino group, and the like.
  • those having a (meth) acryloyloxy group in the molecule include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and propioxyethyl (meth) acrylate.
  • Examples of the monomers other than the monomers (a) to (c) include ethylenically unsaturated monomers copolymerizable with the monomers (a) to (c).
  • Examples of such a monomer include (meth) acrylic acid esters other than the general formula (3), vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, and the like.
  • the (meth) acrylic acid ester means an acrylic acid ester or a metaacrylic acid ester.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth).
  • vinyl compound examples include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone. Be done.
  • aromatic compound examples include styrene, vinyltoluene, ⁇ -methylstyrene and the like.
  • dialkyl ester compound of dibasic acid examples include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
  • the copolymer A can be obtained by copolymerizing the first monomer mixture.
  • the copolymerization is carried out, for example, in the presence of a polymerization initiator.
  • the weight average molecular weight of the copolymer A is 5000 to 300,000. This is because if the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels or cracks, and if it exceeds 300,000, the viscosity of the copolymer solution increases and handling becomes difficult. ..
  • polymerization initiator used in the polymerization reaction examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, and dimethyl-2,2'.
  • -Azo compounds such as azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, tert-butylperoctate, tert-butylperoxy Peroxide of 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, etc.
  • polymerization initiators can be used alone or in combination of two or more.
  • AIBN tert-butylperoctate
  • 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferable.
  • the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like. Of these, solution polymerization is particularly preferable in that the copolymer A can be obtained easily and accurately.
  • an organic solvent may be used if necessary.
  • the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl.
  • Alcohol-based solvents such as alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned.
  • ester-based solvents are particularly preferable, and butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, toluene, and xylene are more preferable.
  • These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 70 to 140 ° C., preferably 80 to 130 ° C.
  • the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
  • the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • antifouling agents include inorganic agents and organic agents.
  • the inorganic drug examples include cuprous oxide, copper thiocyanate (generic name: copper rodan), copper powder and the like.
  • cuprous oxide and copper rodane are particularly preferable, and copper braous oxide that has been surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc., has long-term stability during storage. Is more preferable.
  • organic agents examples include 2-mercaptopyridine-N-copperpyrrhion (generic name: copperpyrityon), 2-mercaptopyridine-N-zinc oxide (generic name: zincpyrityon), and zincethylenebisdithiocarbamate (generic name: geneb ), 4,5-Dichloro-2-n-octyl-3-isothiazolone (generic name: Seanine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: Irgalol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4- [1- (2,3-Dimethylphenyl) ethyl] -1H-imidazo
  • the content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60% by mass, preferably 1 to 50% by mass in terms of solid content.
  • the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and here. It may be in the range between any two of the illustrated values.
  • the upper coating film of the present invention may contain an elution adjuster, a plasticizer, a pigment, a dye, an antifoaming agent, a filler, a dehydrating agent, a shaking agent and the like, if necessary.
  • dissolution modifier examples include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof.
  • monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof.
  • metal salts thereof examples include a salt or the alicyclic hydrocarbon resin. These can be used alone or in combination of two or more.
  • rosin derivative examples include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
  • commercially available alicyclic hydrocarbon resin examples include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Corporation) and the like.
  • plasticizer examples include phosphoric acid ester, phthalate ester, adipate ester, sebacic acid ester, epoxidized soybean oil, alkyl vinyl ether polymer, polyalkylene glycol, t-nonyl pentasulfide, vaseline, and polybutene. , Trisyl trimellitic acid (2-ethylhexyl), silicone oil, liquid paraffin, chlorinated paraffin and the like. These can be used alone or in combination of two or more.
  • Examples of the filler include an inorganic filler and / or an organic filler.
  • Examples of the inorganic filler include calcium carbonate, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, precipitated barium sulfate, barite powder, titanium oxide, calcined kaolin, calcined kaolin surface-treated with aminosilane, silica soil, and water.
  • the organic filler include synthetic resin powders such as polypropylene, polyvinyl chloride, polystyrene, and acrylic silicone.
  • dehydrating agent examples include synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.
  • the antifouling coating composition for the upper coating film can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer A, an antifouling agent, other additives and the like using a disperser.
  • a mixed solution it is preferable that various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent.
  • the disperser for example, one that can be used as a fine pulverizer can be preferably used.
  • a commercially available homomixer, sand mill, bead mill or the like can be used.
  • the mixed solution may be mixed and dispersed by using a container provided with a stirrer to which glass beads or the like for mixing and dispersing are added.
  • the upper coating film contains copolymer B and an antifouling agent.
  • the underlayer coating film can be formed by using an antifouling coating composition obtained by dissolving or dispersing the components contained in the underlayer coating film in a solvent.
  • Copolymer B is a copolymer of the second monomer mixture.
  • the second monomer mixture contains at least one of the monomer (a) and the monomer (b).
  • the second monomer mixture may contain only one of the monomers (a) and (b), or may contain both.
  • the second monomer mixture may contain the monomer (c) or may contain a monomer other than the monomers (a) to (c).
  • the description of the monomers (a) to (c) and other monomers is the same as that of the copolymer A.
  • the copolymer B is a copolymer other than the copolymer A, and when the second monomer mixture is 100% by mass, the total content of the monomer (a) and the monomer (b) is It is 46 to 65% by mass. Specifically, the total content is, for example, 46, 50, 55, 60, 65% by mass, and may be in the range between any two of the numerical values exemplified here.
  • the content of the monomer (a) is, for example, 0 to 65% by mass, and specifically, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55. , 60, 65% by mass, and may be within the range between any two of the numerical values exemplified here.
  • the content of the monomer (b) is, for example, 0 to 65% by mass, and specifically, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55. , 60, 65% by mass, and may be within the range between any two of the numerical values exemplified here.
  • the content of the monomer (c) is, for example, 0 to 54% by mass, and specifically, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 54 mass. %, Which may be within the range between any two of the numerical values exemplified here.
  • the copolymer B can be obtained by copolymerizing the second monomer mixture.
  • the explanation of the physical properties of the copolymer B and the production method is the same as that of the copolymer A.
  • Anti-fouling agent The description of the antifouling agent is the same as that of the upper coating film.
  • the antifouling agent for the upper coating film and the lower coating film may be the same or different.
  • the lower coating film of the present invention may contain an elution adjuster, a plasticizer, a pigment, a dye, an antifoaming agent, a filler, a dehydrating agent, a shaking agent and the like, if necessary. These explanations are the same as those of the upper coating film.
  • the antifouling coating composition for the underlayer coating film can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer B, an antifouling agent, other additives and the like using a disperser. Other explanations are the same as those of the upper coating film.
  • the multi-layer antifouling coating film of the present invention can be obtained by forming an upper layer coating film on a lower layer coating film.
  • the lower coating film and the upper coating film can be formed by applying the antifouling coating composition to the surface (whole or part) of the coating film to be formed, respectively.
  • the coating method include a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method and the like. These may be performed alone or in combination of two or more. After application, dry.
  • the drying temperature may be room temperature.
  • the drying time may be appropriately set according to the thickness of the coating film and the like.
  • the thickness of the undercoat film may be appropriately set according to the type of the coating film to be formed and the like, and is usually 50 to 500 ⁇ m, preferably 100 to 200 ⁇ m.
  • the thickness of the upper coating film may be appropriately set according to the navigation speed of the ship, the seawater temperature, etc., and is usually 50 to 500 ⁇ m, preferably 100 to 200 ⁇ m.
  • the coating film formed product is, for example, an antifouling coating film applied to the surface of a ship (particularly the bottom of a ship), a fishing tool, an underwater structure, or the like, and is an old coating film after being used in seawater for a certain period of time. Can be mentioned.
  • % In each production example, example and comparative example indicates weight%.
  • the viscosity is a value measured at 25 ° C. and is a value obtained by a B-type viscometer.
  • the weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC.
  • the conditions of GPC are as follows.
  • Copper oxide Product name "NC-301" (manufactured by Nissin Chemco Co., Ltd.) Copper pyrithion: Product name “Copper Omagin” (manufactured by Arch Chemical Co., Ltd.) Econia: Product name “Econea 028” ... 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP) Medetomidine: Product name "4- (1- (2,3-Dimethylphenyl) ethyl) -1H-imidazole” (manufactured by Wako Pure Chemical Industries, Ltd.)
  • Tetraethoxysilane trade name "Tetraethyl Orthosilicate” (manufactured by Tokyo Kasei Co., Ltd.)
  • Aliphatic amide-based shaker Brand name "Disparon A603-20X” (manufactured by Kusumoto Kasei Co., Ltd.)
  • Test Example 1 (Impact resistance test) >> A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of seawater constant and an automatic pH controller for keeping the pH of seawater constant were installed. A test plate was prepared according to the following method.
  • a rust-preventive coating (vinyl-based A / C) was applied onto a steel plate (75 ⁇ 150 ⁇ 1 mm) so that the thickness after drying was about 50 ⁇ m, and dried to form a rust-preventive coating. Then, a coating composition for a lower layer coating film was applied onto the rust preventive coating film so that the thickness after drying was about 150 ⁇ m. The obtained coating material was dried at room temperature for 24 hours, and then the coating composition for the upper coating film was applied so that the thickness after drying was 150 ⁇ m. The obtained multi-layer coating film was dried at 40 ° C. for 3 days to prepare a test plate having a dry multi-layer coating film having a thickness of about 300 ⁇ m.
  • the prepared test plate was fixed to the rotating drum of the rotating device so as to come into contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During that time, the temperature of the seawater was maintained at 25 ° C. and the pH was maintained at 8.0 to 8.2, and the seawater was replaced every week. After 36 months from the start of the rotary test, the test plate was washed and dried with water, and then an impact resistance test was performed. Measurements were carried out using falling ball conditions in accordance with JIS K5600-5-3: 1999 "General paint test method-Mechanical properties of coating film-Weight drop resistance". As a result, the state of the coating film due to the impact of the tip of the weight was judged according to the following criteria. ⁇ : No cracking or peeling of the coating film ⁇ : Mild cracking or peeling is observed ⁇ : Moderate cracking or peeling is observed ⁇ : Severe cracking or peeling is observed
  • Test Example 2 (Anti-fouling test) >> A coating composition for a lower coating film was applied to both sides of a hard vinyl chloride plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness of the dry coating film was about 100 ⁇ m. The obtained coating film was dried at room temperature for 24 hours, and a coating composition for an upper coating film was applied onto the dried coating film so as to have a thickness of about 100 ⁇ m. The obtained multi-layer coating material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry multi-layer coating film having a thickness of about 200 ⁇ m. This test plate was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and the stain on the test plate due to deposits was observed for 24 months.
  • ⁇ Level where no polluted organisms such as shellfish and algae adhere and almost no slime adheres
  • ⁇ No adherence of polluted organisms such as shellfish and algae, and slime is thin (to the extent that the coating surface can be seen)
  • ⁇ There is no adhesion of polluted organisms such as shellfish and algae, but slime is thinly attached (to the extent that the coated surface can be seen) and cannot be wiped off strongly with a brush.
  • Level ⁇ There is no adhesion of polluted organisms such as shellfish and algae, but slime is adhered so thick that the coated surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
  • Level of algae There is no adhesion of polluted organisms such as shellfish and algae, but slime is adhered so thick that the coated surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
  • the multi-layer antifouling coating film of all the examples was very excellent in impact resistance and antifouling property.
  • the multi-layer antifouling coating film of all the comparative examples did not have good impact resistance or antifouling property.
  • Comparative Example 1 the silyl ester content in the lower coating film was low, the coating film renewal in the latter half was slightly reduced, a skeleton layer was formed, and the coating film was fragile.
  • Comparative Example 2 the hydrophobicity of the upper coating film was high and the initial coating film dissolution was small, so that the initial antifouling property was poor.
  • Comparative Example 3 since the monomer (c) component constituting the copolymer in the upper coating film was small, the initial coating film dissolution was small and the initial antifouling property was poor.
  • Comparative Example 4 the upper layer was a coating film made of a copolymer of triisopropylsilyl acrylate, and cracks occurred in the latter half, so that the antifouling property was deteriorated and the coating film strength was also lowered.
  • Comparative Example 5 the silyl ester content in the upper coating film was low, proper coating film renewal could not be obtained from the initial stage, the antifouling property was inferior, and the coating film was also fragile.
  • Comparative Example 6 was a coating film made of a copolymer containing none of the monomers (a) to (c), and was inferior in initial antifouling property and coating film strength. In Comparative Example 7, since the silyl ester content in the lower coating film was too high, the coating film was renewed slowly in the latter half, and the antifouling property deteriorated at once.

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Abstract

L'invention concerne un revêtement antisalissure multicouches ayant une excellente résistance au choc et ayant des propriétés antisalissure en immersion à un stade précoce et des propriétés antisalissure à long terme qui sont dans chaque cas excellentes.　Le revêtement antisalissure multicouches selon la présente invention comprend un revêtement de couche inférieure et un revêtement de couche supérieure formé sur celui-ci. Dans le film de revêtement antisalissure multicouches, le revêtement de couche supérieure contient un copolymère A, le revêtement de couche inférieure contient un copolymère B et le revêtement de couche supérieure et le revêtement de couche inférieure contiennent chacun un agent chimique antisalissure. Le copolymère A est un copolymère comprenant un premier mélange de monomères, qui contient un monomère (a) et un monomère (c) et qui peut également contenir un monomère (b). Le copolymère B est un copolymère comprenant un second mélange de monomères contenant au moins l'un du monomère (a) et du monomère (b). Les monomères (a) à (c) sont représentés respectivement par les formules (1) à (3). Dans le copolymère A, lorsque le premier mélange de monomères représente 100 % en masse, la teneur du monomère (a) est de 10 à 45 % en masse, la teneur du monomère (b) est de 0 à 15 % en masse, la teneur du monomère (c) est de 20 à 50 % en masse et la teneur totale du monomère (a) et du monomère (b) est de 10 à 45 % en masse. Dans le copolymère B, qui est un copolymère qui est différent du copolymère A, lorsque le second mélange de monomères représente 100 % en masse, la teneur totale du monomère (a) et du monomère (b) est de 46 à 65 % en masse.
PCT/JP2020/019578 2019-05-22 2020-05-18 Revêtement antisalissure multicouches et objet revêtu portant ledit revêtement sur une surface Ceased WO2020235516A1 (fr)

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