WO2018221642A1 - Revêtement antisalissure multicouche, substrat équipé d'un revêtement antisalissure multicouche et son procédé de production, kit de matériau de revêtement permettant de former un revêtement antisalissure multicouche, composition de matériau de revêtement antisalissure de couche supérieure et procédé antisalissure - Google Patents

Revêtement antisalissure multicouche, substrat équipé d'un revêtement antisalissure multicouche et son procédé de production, kit de matériau de revêtement permettant de former un revêtement antisalissure multicouche, composition de matériau de revêtement antisalissure de couche supérieure et procédé antisalissure Download PDF

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Publication number
WO2018221642A1
WO2018221642A1 PCT/JP2018/020923 JP2018020923W WO2018221642A1 WO 2018221642 A1 WO2018221642 A1 WO 2018221642A1 JP 2018020923 W JP2018020923 W JP 2018020923W WO 2018221642 A1 WO2018221642 A1 WO 2018221642A1
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WO
WIPO (PCT)
Prior art keywords
antifouling
antifouling coating
coating film
organic
laminated
Prior art date
Application number
PCT/JP2018/020923
Other languages
English (en)
Japanese (ja)
Inventor
聡一郎 谷野
Original Assignee
中国塗料株式会社
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Filing date
Publication date
Application filed by 中国塗料株式会社 filed Critical 中国塗料株式会社
Priority to KR1020197034774A priority Critical patent/KR102340452B1/ko
Priority to JP2019521294A priority patent/JP6948391B2/ja
Priority to SG11201911459UA priority patent/SG11201911459UA/en
Priority to CN201880035121.6A priority patent/CN110709484A/zh
Publication of WO2018221642A1 publication Critical patent/WO2018221642A1/fr

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Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • 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
    • C09D5/1637—Macromolecular compounds
    • 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
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a laminated antifouling coating, a substrate with a laminated antifouling coating and a method for producing the same, a coating kit for forming a laminated antifouling coating, an upper antifouling coating composition, and an antifouling method.
  • organic antifouling agents for example, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as Patent Document 1) And 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT) described in Patent Document 2.
  • Patent Document 3 discloses an antifouling coating composition containing two or more types of antifouling agents containing tralopyryl and an acrylic resin having a specific group in the side chain.
  • the antifouling coating composition containing such an antifouling agent and a hydrolyzable polymer, particularly when the antifouling agent is an organic antifouling agent that is soluble in a solvent usually contained in the antifouling coating composition.
  • the antifouling agent is unevenly distributed near the surface of the coating film in the case of drying in the external environment, particularly at a high temperature. There was a problem that occurred. The exact cause of this is unknown, but if the antifouling agent is unevenly distributed near the surface of the paint film, in addition to malfunctions such as abnormal appearance of the paint film, a major problem is the renewal of the paint film at the initial stage of use of the paint film.
  • the present invention has no problem such as poor appearance due to uneven distribution of the antifouling agent on the surface of the coating film, and can exhibit a high antifouling performance for a long time even under a high fouling load.
  • An object is to provide an antifouling coating, a substrate with a laminated antifouling coating using the laminated antifouling coating, a method for producing the same, and an antifouling method. It is another object of the present invention to provide a laminate antifouling coating film forming coating kit and an upper antifouling coating composition that are used in the production of the antifouling coating film.
  • the organic antifouling agent (B1) comprises 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and 4,5-dichloro-2-n-octyl.
  • a laminated antifouling coating film which is at least one selected from -4-isothiazolin-3-one.
  • the laminated antifouling coating film according to [2], wherein the silyl ester group-containing monomer (a11) is represented by the following formula (1-1).
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 , R 13 and R 14 each independently represents a monovalent hydrocarbon group.
  • the hydrolyzable polymer (A1) and / or the hydrolyzable polymer (A2) has structural units derived from the metal ester group-containing monomer (a12).
  • the metal ester group-containing monomer (a12) includes a monomer (a121) represented by the following formula (1-2) and a monomer (a122 represented by the following formula (1-3):
  • each R 21 independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents a metal.
  • R 31 represents a monovalent group containing a terminal ethylenically unsaturated group
  • R 32 is a monovalent organic group having 1 to 30 carbon atoms which does not contain a terminal ethylenically unsaturated group
  • M represents a metal.
  • the organic antifouling agent (B1) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and 4,5 -Dichloro-2-n-octyl-4-isothiazolin-3-one
  • the upper antifouling coating composition (y) comprises a hydrolyzable polymer (A2) and an organic solvent (C2 ) Containing a laminated antifouling coating film-containing substrate.
  • the organic solvent (C2) contains one or more selected from the group consisting of hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, and ester-based organic solvents, [9] or [10] The method for producing a substrate with a laminated antifouling coating film according to [10].
  • the upper antifouling coating composition (y) comprises 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and 4,5-dichloro-
  • An upper antifouling coating composition that is coated on the surface of the lower antifouling coating film (X) containing the hydrolyzable polymer (A1) and the organic antifouling agent (B1),
  • the coating composition contains a hydrolyzable polymer (A2) and an organic solvent (C2), and the organic antifouling agent (B1) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) ) -1H-pyrrole-3-carbonitrile and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the organic solvent (C2) is the lower layer coating
  • An upper-layer antifouling paint composition that is soluble in the organic antifouling agent (B1) contained in the film (X).
  • the present invention there is no problem such as poor appearance due to uneven distribution of the antifouling agent on the surface of the coating film, and a laminated antifouling coating film that exhibits high antifouling performance over a long period even under a high fouling load,
  • a substrate with a laminated antifouling coating using the laminated antifouling coating a method for producing the same, and an antifouling method.
  • the laminated antifouling coating film of the present invention is a laminated antifouling coating film (X) and an upper antifouling coating film (Y) laminated together, and the lower antifouling coating film (X ) Contains a hydrolyzable polymer (A1) and an organic antifouling agent (B1), the upper antifouling coating film (Y) contains a hydrolyzable polymer (A2), and the organic antifouling agent (B1).
  • the soil agent (B1) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and 4,5-dichloro-2-n-octyl-4- At least one selected from isothiazolin-3-one.
  • the base material with a laminated antifouling coating film of the present invention is formed by coating the base material with the laminated antifouling coating film of the present invention.
  • stacking antifouling coating film of this invention apply
  • the lower antifouling coating composition (x) has a step of applying an upper antifouling coating composition (y) on the lower antifouling coating (X) to form an upper antifouling coating (Y).
  • the substrate with a laminated antifouling coating film of the present invention is preferably produced by the method for producing a substrate with a laminated antifouling coating film of the present invention.
  • the laminated antifouling coating film of the present invention is formed by the lower antifouling coating composition (x) and the upper antifouling coating composition (y) used in the method for producing a substrate with the laminated antifouling coating. It is preferable.
  • the present invention there is no problem such as poor appearance due to uneven distribution of the antifouling agent on the surface of the coating film, and a laminated antifouling coating film that exhibits high antifouling performance over a long period even under a high fouling load,
  • a substrate with a laminated antifouling coating using the laminated antifouling coating a method for producing the same, and an antifouling method.
  • the organic antifouling agent (B1) contained in the lower antifouling coating film (X) was unevenly distributed in the vicinity of the surface of the lower antifouling coating film (X) when forming the lower antifouling coating film (X). Even in the case, by providing the upper antifouling coating film (Y) on the lower antifouling coating film (X), the organic antifouling agent (B1) as a whole laminated antifouling coating film is brought close to the surface. It is considered that uneven distribution is suppressed and occurrence of appearance defects is suppressed.
  • the organic antifouling agent (B1) is continuously supplied from the lower antifouling coating film (X) into the upper antifouling coating film (Y). Therefore, it is estimated that high antifouling performance can be exhibited over a long period of time. Since the lower antifouling coating film (X) and the upper antifouling coating film (Y) both contain a hydrolyzable polymer, the lower antifouling coating film (X) and the upper antifouling coating film (Y) The antifouling property is also exerted by the coating film renewability.
  • the upper antifouling coating composition (y) for forming the upper antifouling coating (Y) contains the organic solvent (C2), and the organic solvent (C2) is the lower antifouling coating (X).
  • the upper antifouling coating composition (y) is applied to the lower antifouling coating film (X)
  • the upper antifouling coating composition (y) Since the organic antifouling agent (B1) is extracted therein and an appropriate amount of the organic antifouling agent (B1) is supplied into the upper antifouling coating film (Y), it exhibits high antifouling performance from the beginning. Is estimated to be possible.
  • the organic antifouling agent is uniformly distributed, or compared with the antifouling coating film that is unevenly distributed toward the surface layer, the laminated antifouling coating of the present invention
  • the film is considered to have a concentration gradient state in which the concentration of the organic antifouling agent (B1) increases toward the lower layer, and the upper layer in terms of disappearance due to diffusion of the organic antifouling agent from the coating film in water. It is also presumed that the antifouling performance is improved because the concentration of the organic antifouling agent (B1) can be kept high when the coating film renewal toward the lower layer reaches the lower layer.
  • the lower antifouling coating film (X), the lower antifouling coating composition (x) suitable for forming the lower antifouling coating (X), the upper antifouling coating (Y), and the upper antifouling coating The upper antifouling paint composition (y) suitable for forming the dirty coating film (Y) will be described.
  • the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) are collectively referred to as an antifouling paint composition or a paint composition.
  • the hydrolyzable polymer contained in the lower layer antifouling paint composition (x) is a hydrolyzable polymer (A1)
  • the hydrolyzable polymer contained in the upper layer antifouling paint composition (y) is hydrolysable.
  • each component contained in the lower layer antifouling paint composition (x) includes 1 after the alphabet representing the component, and each component contained in the upper layer antifouling paint composition (y).
  • 2 is added after the alphabet representing the component, and when these are collectively referred to, they are described without a numeral as in the hydrolyzable polymer (A).
  • the laminated antifouling coating film of the present invention is formed by laminating a lower antifouling coating film (X) and an upper antifouling coating film (Y).
  • the lower antifouling coating film (X) and the upper antifouling coating film (Y) are preferably adjacent layers.
  • the lower antifouling coating film (X) contains a hydrolyzable polymer (A1) and an organic antifouling agent (B1), and the upper antifouling coating film (Y) contains a hydrolyzable polymer (A2). To do.
  • the lower layer antifouling coating composition (x) suitably used for forming the lower layer antifouling coating film (X) contains a hydrolyzable polymer (A1) and an organic antifouling agent (B1), and It is preferable to contain an organic solvent (C1).
  • the upper antifouling coating film (Y) contains a hydrolyzable polymer (A2).
  • the upper antifouling coating composition (y) suitably used for forming the upper antifouling coating film (Y) may contain an organic solvent (C2) in addition to the hydrolyzable polymer (A2). preferable.
  • the lower antifouling coating film (X) contains a hydrolyzable polymer (A1)
  • the upper antifouling coating film (Y) contains a hydrolyzable polymer (A2).
  • the hydrolyzable polymer (A1) and the hydrolyzable polymer (A2) are collectively referred to as a hydrolyzable polymer (A).
  • the lower layer antifouling coating film (X) and the upper layer antifouling coating film (Y) contain the hydrolyzable polymer (A), so that the antifouling coating film has appropriate water resistance and antifouling property due to coating film renewability. Is granted.
  • the hydrolyzable polymer (A) has a structural unit derived from (i) a hydrolyzable group-containing monomer (a1), and (ii) a structure derived from another monomer (a2). It is preferable to have a unit.
  • the “polymer having a structural unit derived from a” means a polymer in which a is introduced by a polymerization reaction or chain transfer.
  • the hydrolyzable polymer is such that the radical polymerization terminal pulls out H of —SH and the generated —S ⁇ (S radical) starts polymerization.
  • the hydrolyzable polymer (A) also has a structural unit derived from the other monomer (a2).
  • each structural unit will be described.
  • the hydrolyzable polymer (A) has a structural unit derived from (i) the hydrolyzable group-containing monomer (a1).
  • Preferred examples of the hydrolyzable group-containing monomer (a1) include a silyl ester group-containing monomer (a11) or a metal ester group-containing monomer (a12).
  • the antifouling coating composition contains the hydrolyzable polymer (A) having a structural unit derived from the silyl ester group-containing monomer (a11), the antifouling property and upper layer of the laminated antifouling coating film to be formed This is preferable from the viewpoint of improving the interlayer adhesion between the antifouling coating film (Y) and the lower antifouling coating film (X).
  • the antifouling property of the laminated antifouling coating film to be formed also includes that the antifouling coating composition contains a hydrolyzable polymer (A) having a structural unit derived from the metal ester group-containing monomer (a12). And from the viewpoint of improving the coating film properties of the antifouling coating film.
  • the content of the structural unit derived from the hydrolyzable monomer (a1) in the hydrolyzable polymer (A) is preferably 3 to 3 when the total structural unit of the hydrolyzable polymer is 100 parts by mass. 80 parts by mass, more preferably 5 to 70 parts by mass.
  • silyl ester group-containing monomer (a11) preferably contains a compound represented by the following formula (1-1).
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 , R 13 and R 14 each independently represents a monovalent hydrocarbon group.
  • R 11 represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving the long-term antifouling property and water resistance of the antifouling coating film.
  • R 12 , R 13 and R 14 each independently represent a monovalent hydrocarbon group, and examples of such hydrocarbon groups include linear, branched or cyclic alkyl groups. , And aryl groups.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • R 12 to R 14 are isopropyl group, n-propyl group, sec-butyl group, It is preferably selected from an n-butyl group and a phenyl group, more preferably all of R 12 to R 14 are isopropyl groups. That is, as the silyl ester group-containing monomer (a11), triisopropylsilyl (meth) acrylate is particularly preferable, and triisopropylsilyl methacrylate is most preferable.
  • the hydrolyzable polymer (A) has a structural unit derived from the monomer (a11)
  • the amount of the structural unit derived from the monomer (a11) with respect to 100 parts by mass of all the structural units is antifouling coating.
  • it is preferably 10 to 90 parts by mass, more preferably 40 to 80 parts by mass, still more preferably 45 to 70 parts by mass, and even more preferably 45 to 65 parts by mass.
  • the ratio of each content (mass) of the structural unit derived from each monomer etc. in a hydrolyzable polymer (A) is the preparation amount of each said monomer etc. (reaction raw material) used for a polymerization reaction. It can be regarded as the same as the ratio of (mass).
  • the hydrolyzable group-containing monomer (a1) preferably contains a metal ester group-containing monomer (a12), and the metal ester group-containing monomer is represented by the following formula (1-2): It is preferable to contain at least one of a monomer (a121) represented by the formula (1) and a monomer (a122) represented by the following formula (1-3).
  • each R 21 independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents a metal.
  • Examples of the metal constituting the metal ester group include magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, and aluminum.
  • M is a divalent metal, and a divalent metal can be appropriately selected from the metals described above.
  • Group 10-12 metals such as nickel, copper, and zinc are preferred, copper and zinc are more preferred, and zinc is even more preferred.
  • R 21 represents a monovalent group containing a terminal ethylenically unsaturated group (CH 2 ⁇ C ⁇ ), and the carbon number of R 21 is preferably 2 to 50, more preferably Is 2 to 30, more preferably 2 to 10, and still more preferably 2 to 6.
  • R 21 only needs to have a terminal ethylenically unsaturated group, and may have an ethylenically unsaturated group other than the terminal, but may have an ethylenically unsaturated group only at the terminal. More preferred.
  • R 21 is preferably an unsaturated aliphatic hydrocarbon group containing a terminal ethylenically unsaturated group, and the unsaturated aliphatic hydrocarbon group has an ester bond, an amide bond, or an ether bond in the carbon chain. You may have.
  • R 21 examples include acrylic acid (2-propenoic acid), methacrylic acid (2-methyl-2-propenoic acid), 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, 3- (meth)
  • examples thereof include a group obtained by removing a carboxy group from an aliphatic unsaturated monocarboxylic acid having a terminal ethylenically unsaturated group such as acryloyloxypropionic acid and 3- (meth) acryloyloxy-2-methylpropionic acid.
  • R 21 is preferably a group obtained by removing a carboxy group from an aliphatic unsaturated monocarboxylic acid containing a terminal ethylenically unsaturated group, and includes acrylic acid, methacrylic acid, and (meth) acryloyloxyalkyl.
  • a group obtained by removing a carboxy group from a carboxylic acid is more preferred, and a group obtained by removing a carboxy group from acrylic acid or methacrylic acid is more preferred.
  • Such a monomer (a121) is preferably a monomer (a121 ') represented by the following formula (1-2').
  • R 22 each independently represents a hydrogen atom or a methyl group, and M ′ represents copper or zinc.
  • the monomer (a121) represented by the formula (1-2) zinc diacrylate, zinc dimethacrylate, zinc acrylate (methacrylic acid), zinc di (3-acryloyloxypropionate), di (3 -Methacryloyloxypropionic acid) zinc, di (3- (meth) acryloyloxy-2-methylpropionic acid) zinc, copper diacrylate, copper dimethacrylate, acrylic acid (methacrylic acid) copper, di (3-acryloyloxypropion) Acid) copper, di (3-methacryloyloxypropionic acid) copper, and di (3- (meth) acryloyloxy-2-methylpropionic acid) copper.
  • R 31 represents a monovalent group containing a terminal ethylenically unsaturated group
  • R 32 is a monovalent organic group having 1 to 30 carbon atoms which does not contain a terminal ethylenically unsaturated group
  • M represents a metal.
  • R 31 represents a monovalent group containing a terminal ethylenically unsaturated group.
  • R 31 include the same groups as R 21 in formula (1-2), and preferred embodiments are also the same.
  • R 32 represents a monovalent organic group having 1 to 30 carbon atoms that does not contain a terminal ethylenically unsaturated group.
  • R 32 includes an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aromatic hydrocarbon having 6 to 30 carbon atoms, which does not contain a terminal ethylenically unsaturated group. Examples are groups. These groups may have a substituent.
  • the substituent examples include a hydroxyl group.
  • the aliphatic hydrocarbon group may be linear or branched, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. When R 32 is an unsaturated aliphatic hydrocarbon group, R 32 does not contain a terminal ethylenically unsaturated group.
  • the aliphatic hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 28 carbon atoms, more preferably 1 to 26 carbon atoms, and still more preferably 1 to 24 carbon atoms.
  • the aliphatic hydrocarbon group may be further substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
  • the alicyclic hydrocarbon group may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group has 3 to 30, preferably 4 to 20, more preferably 5 to 16, and still more preferably 6 to 12 carbon atoms.
  • the alicyclic hydrocarbon group may be further substituted with an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group has 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • the aromatic hydrocarbon group may be further substituted with an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
  • R 32 is preferably an organic acid residue formed from a monobasic acid, specifically, versatic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, Examples thereof include a group in which a carboxy group is removed from an organic acid selected from the group consisting of neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid. Among these, a group obtained by removing a carboxy group from abietic acid, versatic acid, and naphthenic acid is preferable, and a group obtained by removing a carboxy group from abietic acid and versatic acid is more preferable.
  • Such a monomer (a122) is preferably a monomer (a122 ') represented by the following formula (1-3').
  • R 33 represents a hydrogen atom or a methyl group
  • R 34 represents a monovalent organic group having 1 to 30 carbon atoms that does not contain a terminal ethylenically unsaturated group
  • M ′ represents (Indicates copper or zinc.)
  • Examples of the monomer (a122) represented by the formula (1-3) include 3- (meth) acryloyloxypropionic acid (rosin) zinc, 3- (meth) acryloyloxypropionic acid (versaic acid) zinc, ) Zinc acrylic acid (rosin), (meth) acrylic acid (versaic acid) zinc, (meth) acrylic acid (naphthenic acid) zinc, 3- (meth) acryloyloxypropionic acid (rosin) copper, 3- (meth) acryloyl Examples include oxypropionic acid (versaic acid) copper, (meth) acrylic acid (rosin) copper, (meth) acrylic acid (versatic acid) copper, and (meth) acrylic acid (naphthenic acid) copper.
  • the hydrolyzable polymer (A) has a structural unit derived from the monomer (a122) represented by the formula (1-3), the hydrolyzable polymer (A) is represented by the formula (1-3 It is preferable to have a structural unit obtained by polymerization of only the terminal ethylenically unsaturated group in the polymerizable compound represented by (monomer (a122)).
  • hydrolyzable polymer (A) has a structural unit derived from monomer (a121) or (a122), a structure derived from monomers (a121) and (a122) with respect to 100 parts by mass of all structural units
  • the total content of units is preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, from the viewpoint of improving the antifouling performance and water resistance of the antifouling coating film.
  • the hydrolyzable polymer (A) preferably has a structural unit derived from (ii) another monomer (a2).
  • the monomer copolymerizable with the said monomer (a1) can be used without a restriction
  • another monomer (a2) is an ethylenically unsaturated compound.
  • Examples of the other monomer (a2) include: Polyorganosiloxane block-containing monomer (a21); Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl ( (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate Alkyl (meth) acrylates such as lauryl (meth) acrylate, cetyl
  • the polyorganosiloxane block-containing monomer (a21) is a monomer having a polyorganosiloxane block and a chain transfer reactive group such as a polymerizable unsaturated group and / or a thiol group.
  • a polyorganosiloxane block is introduced into the degradable polymer (A), which is particularly preferable in terms of improving antifouling performance such as slime resistance.
  • the polyorganosiloxane block-containing monomer (a21) is preferably represented by the following formula (2).
  • R 1 , R 2 and R 3 each independently represents a monovalent hydrocarbon group
  • X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group
  • n is 0 or more
  • p and q are each independently 0 or 1
  • n + p + q is 1 or more.
  • R 1 , R 2 , and R 3 each independently represent a monovalent hydrocarbon group, and the hydrocarbon group is a linear, branched, or cyclic alkyl group, and an aryl group.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • R 1 , R 2 , and R 3 are preferably alkyl groups such as a methyl group and a butyl group from the viewpoint of ease of polymerization.
  • each X independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and is preferably a (meth) acryloyloxyalkyl group from the viewpoint of uniform polymerization, and the viscosity of the polymer to be formed Mercaptoalkyl groups are also preferred from the standpoint of reducing the amount and facilitating handling.
  • Examples of such X include (meth) acryloyloxyethyl group, (meth) acryloyloxypropyl group, (meth) acryloyloxybutyl group, mercaptomethyl group, mercaptoethyl group, mercaptopropyl group, mercaptobutyl group and the like.
  • m is 1 or more
  • n is 0 or more
  • p and q are each independently 0 or 1
  • n + p + q is 1 or more.
  • m and n mean the average number of repetitions of (SiR 2 2 O) and (SiXR 3 O), respectively.
  • m + n is preferably 2 or more.
  • repeating units when two or more different repeating units are described in parallel between [], these repeating units are respectively repeated in any form and order of random, alternating or block. Indicates that it may be. That is, for example, in the formula-[Y 3 -Z 3 ]-(where Y and Z represent repeating units), in a random form such as -YYZYZZ-, in an alternating form such as -YZYZYZ-, A block shape such as YYYZZZZ- or -ZZZYYY- may be used.
  • a hydrolyzable polymer (A) is a structural unit derived from the monomer (a211) whose n is 0, p is 1, and q is 0 in Formula (2). It is preferable to have.
  • the antifouling coating composition containing the hydrolyzable polymer (A) having a structural unit derived from such a monomer (a211) can form an antifouling coating film having particularly excellent antifouling properties. Is preferable.
  • m is preferably from 3 to 200, more preferably from 5 to 70, from the viewpoint of ease of polymerization and the like.
  • a commercially available product can be used.
  • X-22-174ASX single terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 900 g / mol
  • KF-2012 single terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent, manufactured by Shin-Etsu Chemical Co., Ltd. 4,600g / m l
  • X-22-2426 one terminal methacryloyloxyalkyl
  • a hydrolyzable polymer (A) has a structural unit derived from the monomer (a212) whose n is 0 and p and q are 1 in Formula (2).
  • the antifouling coating composition containing the hydrolyzable polymer (A) having a structural unit derived from such a monomer (a212) tends to have good interlayer adhesion of the laminated antifouling coating film to be formed. This is preferable.
  • m is preferably from 3 to 200, more preferably from 5 to 70, from the viewpoint of ease of polymerization and the like.
  • a commercially available product can be used.
  • X-22-164 both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 190 g / mol
  • X-22-164AS both ends methacryloyloxyalkyl-modified organopolysiloxane, functional, manufactured by Shin-Etsu Chemical Co., Ltd.
  • X-22-164A both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 860 g / mol
  • X-22-164B both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 1630 g / mol
  • X -22-164C both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 2,370 g / mol
  • X-22-164E both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 3,900 g / mol
  • X-22-167B both terminal mercaptoalkyl-modified organopolysiloxane, functional group equivalent 1,670 g / mol).
  • the hydrolyzable polymer (A) has a structural unit derived from a monomer (a213) in which X is a mercaptoalkyl group and n is 1 or more in the formula (2). It is also preferable. It is preferable that the hydrolyzable polymer (A) has a structural unit derived from such a monomer (a213) because the viscosity is low and the handling is easy.
  • m is preferably 50 to 1,000 and n is preferably 1 to 30 from the viewpoint of ease of polymerization and the like.
  • a commercially available monomer can be used as such a monomer (a213).
  • KF-2001 side chain mercaptoalkyl-modified organopolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent 1,900 g) / Mol
  • KF-2004 side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent 30,000 g / mol
  • the content of the structural unit derived from the monomer (a21) in the hydrolyzable polymer (A) is all from the viewpoints of antifouling performance, water resistance and interlayer adhesion under alternating wet and dry conditions of the antifouling coating film.
  • the amount is preferably 0.5 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 2 to 50 parts by mass, and still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the structural unit.
  • the hydrolyzable polymer (A) can be obtained by synthesizing the hydrolyzable group-containing monomer (a1) and, if necessary, another monomer (a2) by a known method.
  • a known method for example, when the hydrolyzable group-containing monomer (a1) contains the monomer (a121) or (a122), for example, an inorganic metal compound (preferably an oxide or hydroxide of copper or zinc, Chloride, etc.) and an organic acid such as methacrylic acid or acrylic acid or an esterified product thereof are synthesized by a known method such as heating at a temperature below the decomposition temperature of the metal salt in the presence of an organic solvent and water and stirring. be able to.
  • an inorganic metal compound preferably an oxide or hydroxide of copper or zinc, Chloride, etc.
  • an organic acid such as methacrylic acid or acrylic acid or an esterified product thereof
  • a mixed solution obtained by mixing a solvent and a metal component such as zinc oxide is stirred while being heated to about 50 to 80 ° C., and this is mixed with an organic acid such as methacrylic acid or acrylic acid or its A monomer (a121) or (a122) is prepared by dropping a mixed liquid of an ester body and water and stirring the mixture.
  • a solvent is placed in a newly prepared reaction vessel and heated to about 80 to 120 ° C., and the monomer (a121) or (a122) and other monomers (a2), a polymerization initiator,
  • a metal ester group-containing hydrolyzable polymer (A) can be obtained by dropping a mixed liquid of a chain transfer agent and a solvent and conducting a polymerization reaction.
  • a polymerization initiator which can be used for manufacture of a hydrolysable polymer (A) Various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2′-azobis (isobutyronitrile) [AIBN], 2,2 Examples include '-azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], and tert-butyl peroctoate [TBPO].
  • These polymerization initiators may be used alone or in combination of two or more. These radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added to the reaction system both at the start of the reaction and during the reaction.
  • the amount of the polymerization initiator used in the production of the hydrolyzable polymer (A) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the monomers.
  • the chain transfer agent that can be used for the production of the hydrolyzable polymer (A) is not particularly limited, and examples thereof include ⁇ -methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, ⁇ -terpinene; tert-dodecyl mercaptan. And mercaptans such as n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; and the like. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together. When a chain transfer agent is used in the production of the hydrolyzable polymer (A), the amount used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the above monomers.
  • Examples of the solvent that can be used for the production of the hydrolyzable polymer (A) include aromatic solvents such as toluene, xylene, and mesitylene; propanol, butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like.
  • aromatic solvents such as toluene, xylene, and mesitylene
  • propanol, butanol propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like.
  • Examples include alcohols; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as ethyl acetate and butyl acetate; and water.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable polymer (A) are the viscosity and storage stability of the antifouling coating composition, the dissolution rate (upgradability) of the resulting antifouling coating film, etc. Therefore, it is preferable to adjust appropriately.
  • the number average molecular weight (Mn) is preferably 1,000 to 100,000, more preferably 1,500 to 30,000.
  • the weight average molecular weight (Mw) is preferably 2,000 to 200,000, more preferably 3,000 to 60,000.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by measuring with gel permeation and converting with standard polystyrene.
  • a hydrolyzable polymer (A) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the hydrolyzable polymer (A) in the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) depends on the coating workability of the antifouling paint and the antifouling coating film in the present invention.
  • the solid content of the antifouling coating composition is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass. % Or less, more preferably 90% by mass or less, and still more preferably 88% by mass or less.
  • the above content is hydrolysable. This is a preferable range as the total content of the polymer (A), and the same applies to each component described later.
  • the hydrolyzable polymer (A) has a structural unit derived from the silyl ester group-containing monomer (a11), the solid content of the lower layer antifouling paint composition (x) or the upper layer antifouling paint composition (y)
  • the content of the hydrolyzable polymer (A) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 12 to 40% by mass.
  • the hydrolyzable polymer (A) has a structural unit derived from a metal ester group-containing monomer, preferably the monomer (a121) and / or the monomer (a122), the lower layer antifouling paint composition
  • the content of the hydrolyzable polymer (A) in the solid content of the product (x) or the upper layer antifouling coating composition (y) is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, The content is preferably 20 to 90% by mass, and more preferably 25 to 88% by mass.
  • the hydrolyzable polymer (A) has a structural unit derived from the polyorganosiloxane block-containing monomer (a21), in order to increase the slime resistance estimated to be due to the contribution of the polyorganosiloxane, It is preferable to increase the content ratio of the hydrolyzable polymer (A) in the antifouling coating film.
  • the coating composition contains two or more hydrolyzable polymers (A)
  • the above content is a preferable range as the total content of the hydrolyzable polymer (A), which will be described later. The same applies to each component.
  • the lower antifouling coating film (X) and the lower antifouling coating composition (x) contain an organic antifouling agent (B1), and the organic antifouling agent is 4-bromo-2- (4 -Chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
  • 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile is represented by the following formula (b1) and is also called tralopyryl.
  • 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is represented by the following formula (b2) and is also referred to as DCOIT.
  • the organic antifouling agent (B1) is at least one selected from tralopyril and DCOIT.
  • tralopyril and DCOIT are preferable to contain tralopyril and to prevent the slime that is a cell secretion.
  • DCOIT is included from the viewpoint of improving soiling.
  • An organic antifouling agent (B1) may be used individually by 1 type, and may use 2 or more types together. That is, tralopyril or DCOIT may be used alone, or tralopyril and DCOIT may be used in combination.
  • the total content of the organic antifouling agent (B1) in the lower layer antifouling paint composition (x) can be arbitrarily selected according to the efficacy and cost of the organic antifouling agent used, but the lower layer antifouling paint composition ( x) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably from the viewpoint of imparting excellent antifouling properties and physical properties to the laminated antifouling coating film. 3 to 20% by mass. Further, the total content of the organic antifouling agent (B1) in the lower antifouling coating film (X) is preferably 0.1 to from the viewpoint of imparting excellent antifouling properties and physical properties to the laminated antifouling coating film.
  • the content of the organic antifouling agent (B1) in the lower antifouling coating film (X) is the organic content of the upper antifouling coating composition (y) when the upper antifouling coating film (Y) is formed. It fluctuates with dissolution in the solvent (C2) and supply from the lower antifouling coating (X) to the upper antifouling coating (Y) in the laminated antifouling coating. Therefore, it is most appropriate to define the content of the organic antifouling agent (B1) by the content in the solid content of the lower layer antifouling coating composition (x).
  • the lower-layer antifouling coating composition (x) contains tralopyril as the organic antifouling agent (B1)
  • the lower-layer antifouling coating composition is improved from the viewpoint of improving the antifouling property and coating film properties and interlayer adhesion of the laminated antifouling coating film.
  • the content of tralopyryl in the solid content of the soil coating composition (x) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass.
  • the lower layer coating composition (x) contains DCOIT as the organic antifouling agent (B1)
  • the DCOIT content in the solid content of the lower layer antifouling coating composition (x) is preferably from the same viewpoint. Is 0.5 to 15% by mass, more preferably 1 to 12% by mass, and still more preferably 2 to 10% by mass.
  • the lower layer antifouling paint composition (x) may contain other organic antifouling agent (B′1) as an organic antifouling agent in addition to the above-described tralopyril and DCOIT.
  • the other organic antifouling agent (B′1) is a compound having antifouling properties and containing no metal element. Note that boron, which is a semimetal, does not correspond to a metal element.
  • organic antifouling agents (B′1) include borane-nitrogen base adducts such as pyridine triphenylborane and 4-isopropylpyridinediphenylmethylborane, (+/ ⁇ )-4- [1- (2, 3-dimethylphenyl) ethyl] -1H-imidazole (also known as medetomidine), N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea (also known as diuron), N- (2,4,6-tri Chlorophenyl) maleimide, 2,4,5,6-tetrachloroisophthalonitrile, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine (also known as sibutrin), chloromethyl- n-octyl disulfide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio
  • the upper layer antifouling paint composition (y) is an organic antifouling agent (B2) that is optionally at least one selected from tralopyril and DCOIT, as long as the effects of the present invention are not impaired.
  • An organic antifouling agent (B′2) may be contained.
  • Examples of the other organic antifouling agent (B′2) include the same compounds as the other organic antifouling agent (B′1).
  • the content of the organic antifouling agent (B2) in the upper layer antifouling coating composition (y) is:
  • the content of the organic antifouling agent in the upper antifouling coating film (Y) is preferably an amount that is lower than the content of the organic antifouling agent in the lower antifouling coating film (X).
  • the upper antifouling coating composition (y) preferably does not substantially contain the organic antifouling agent (B2) as described above from the viewpoint of preventing precipitates from forming on the surface of the antifouling coating film.
  • the upper-layer antifouling coating composition (y) contains a hydrolyzable polymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11), the tralopyryl or pyridine triphenyl is used.
  • a hydrolyzable polymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11)
  • the tralopyryl or pyridine triphenyl is used.
  • borane-nitrogen base adducts such as borane and 4-isopropylpyridinediphenylmethylborane
  • nitrogen-containing heterocyclic organic antifouling agents such as medetomidine
  • the upper-layer antifouling paint composition (y) contains the organic antifouling agent (B2) and / or other organic antifouling agent (B′2)
  • the content thereof is the upper-layer antifouling paint composition (y).
  • the solid content is preferably 0.1% by mass to 10% by mass, and more preferably 0.3% by mass to 5% by mass.
  • the upper antifouling coating film (Y) is not only an organic antifouling agent (B2) and other organic antifouling agent (B′2) contained in the upper antifouling coating composition (y), but also an upper antifouling agent.
  • Organic antifouling agent (B1) and other organic antifouling agent (B'1) dissolved from the lower antifouling coating film (X) at the time of applying the coating composition (y) It contains the organic antifouling agent (B1) and other organic antifouling agent (B′1) transferred from the fouling coating (X). Therefore, even if the upper antifouling coating composition (y) does not substantially contain the organic antifouling agent (B2) and the other organic antifouling agent (B′2), the upper antifouling coating film (Y) contains an organic antifouling agent.
  • the upper antifouling coating composition (y) is obtained by extracting the organic antifouling agent (B1) from the lower antifouling coating film (X) and the viscosity of the upper antifouling coating composition (y). It is preferable to contain an organic solvent (C2) for the purpose of adjusting the viscosity.
  • the upper antifouling paint composition (y) may contain the solvent used in preparing the hydrolyzable polymer (A2) as the organic solvent (C2). When mixing A2) and other components as necessary, a separately added solvent may be contained.
  • the organic solvent (C2) is preferably selected from those in which the organic antifouling agent (B1) described above is soluble in the organic solvent (C2).
  • soluble means that the solubility at 23 ° C. is 1 g / L or more.
  • the organic solvent (C2) preferably contains an organic antifouling agent (B1) having a solubility at 23 ° C. of 10 g / L or more, more preferably 100 g / L or more.
  • the solubility can be determined, for example, by the following method. After 100 g of the solute for measuring the solubility and 1 L of the solvent are sufficiently stirred in the container to obtain a uniform suspension, the concentration of the medium in the supernatant can be determined by measuring with a measuring method such as HPLC. When the mixture becomes a uniform solution, the solubility is 100 g / L or more.
  • Organic solvents (C2) include hydrocarbon organic solvents such as xylene, toluene, and ethylbenzene; methyl ethyl ketone, cyclohexanone, 4-methyl-2-pentanone (also known as methyl isobutyl ketone), 2-heptanone (also known as methyl amyl ketone) Ketone organic solvents such as ethanol; aliphatic organic solvents such as ethanol, isopropyl alcohol, n-butanol, isobutanol, propylene glycol monomethyl ether, ethylene glycol, etc.
  • hydrocarbon organic solvents such as xylene, toluene, and ethylbenzene
  • methyl ethyl ketone cyclohexanone
  • 4-methyl-2-pentanone also known as methyl isobutyl ketone
  • 2-heptanone also known as methyl amyl ketone
  • Ketone organic solvents such as
  • ester organic solvents such as ethyl, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate. From the viewpoints of volatilization rate, ease of handling, availability of raw materials, etc., xylene, n- Butanol, isobutanol, propylene Glycol monomethyl ether acetate n- butyl, isobutyl acetate, 2-heptanone is preferred.
  • the organic solvent (C2) contained in the upper antifouling coating composition (y) As the organic solvent (C2) contained in the upper antifouling coating composition (y), the effect of supplying the organic antifouling agent (B1) contained in the lower antifouling coating film to the upper antifouling coating film (Y) is effective. From the viewpoint of making it, it is preferable to contain the ester organic solvent or the ketone organic solvent described above, and it is more preferable to contain the ester organic solvent.
  • the upper layer antifouling paint composition (y) contains an ester organic solvent or a ketone organic solvent as the organic solvent (C2), the content thereof is 1 to 50 mass in the upper layer antifouling paint composition (y). %, Preferably 2 to 30% by mass.
  • the organic antifouling agent (B1) contained in the lower antifouling coating film (X) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as : Tralopyril), in addition to the above-mentioned viewpoint, from the viewpoint of supply of tralopyril to the upper antifouling coating film (Y), in particular, an alcohol organic solvent, an ester organic solvent or a ketone organic solvent as described above is used. In particular, from the viewpoint of reducing the viscosity of the upper antifouling coating composition (y) and facilitating coating workability, it is preferable to include an ester organic solvent.
  • the content in the coating composition (y) is preferably 2 to 50% by mass, and more preferably 5 to 30% by mass.
  • An organic solvent (C2) may be used individually by 1 type, and may use 2 or more types together.
  • the organic solvent (C2) contained in the upper antifouling coating composition (y) is an organic antifouling agent (B1) contained in the lower antifouling coating film (X) and the lower antifouling coating composition (x). ) Is preferably soluble.
  • the organic solvent (C2) is soluble in the organic antifouling agent (B1).
  • the organic solvent (C2) contains two or more organic solvents
  • the organic compound contained in the upper antifouling coating composition (y) which is soluble in an organic solvent having the largest content (mass%), or (ii) is a mixed liquid of two or more organic solvents It means satisfy
  • “soluble” means that the solubility at 23 ° C. is 1 g / L or more, preferably 10 g / L or more, and more preferably 100 g / L or more. preferable.
  • the content of the organic solvent (C2) in the upper-layer antifouling coating composition (y) is selected from the viewpoints of coating workability of the upper-layer coating composition (y), drying properties of the coating film, environmental discharge, and the like.
  • the organic antifouling agent (B1) from the lower antifouling coating film (X) into the upper antifouling coating film (Y) preferably 5 to 90% by mass, more preferably 10 to 90% by mass, The amount is preferably 20 to 80% by mass, and more preferably 40 to 70% by mass.
  • the lower layer antifouling coating composition (x) may also contain an organic solvent (C1).
  • the organic solvent (C1) are the same as the organic solvent (C2) contained in the upper antifouling coating composition (y).
  • the content of the organic solvent (C1) in the lower layer antifouling paint composition (x) is preferably 5 to 90% by mass, more preferably 10 to 70% by mass.
  • the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) may contain other components in addition to the components described above.
  • the coating composition of the present invention may further contain another antifouling agent (D) for the purpose of further improving the antifouling property of the coating film to be formed.
  • the other antifouling agent (D) is an antifouling agent other than the organic antifouling agent (B) and the other organic antifouling agent (B ′).
  • the organic antifouling agent (B), the other organic antifouling agent (B ′), and the other antifouling agent (D) are collectively referred to simply as an antifouling agent.
  • the laminated antifouling coating film of the present invention exhibits excellent antifouling properties by optimal use of the organic antifouling agent (B1) derived from the lower antifouling coating film (X).
  • the coating composition (y) contains the other antifouling agent (D)
  • the antifouling performance can be further improved.
  • the present invention can reduce such an antifouling agent that is originally required to obtain an antifouling performance that can cope with a highly fouling environment. The effect that emission can be reduced can be obtained.
  • the lower layer coating composition (x) contains another antifouling agent (D)
  • good antifouling properties are exhibited in the coating film in a situation where the antifouling property is required for the coating film.
  • antifouling agents (D) include, for example, cuprous oxide, copper oxide, copper (metal copper), copper thiocyanate (also known as rhodan copper), copper pyrithione and zinc pyrithione, and other metal pyrithions, bisdimethyldithiocarbamoyl Zinc ethylene bisdithiocarbamate (also known as polycarbamate), zinc dimethyldithiocarbamate (also known as diram), zinc ethylene bisdithiocarbamate, etc. It is preferable to do.
  • the average particle size of cuprous oxide is preferably about 0.1 to 30 ⁇ m for exhibiting long-term antifouling properties, and the surface is made of glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, etc. What is processed is preferable in terms of long-term stability during storage.
  • examples of such commercially available cuprous oxide include NC-301 (manufactured by NC Tech Co., Ltd.), NC-803 (manufactured by NC Tech Co., Ltd.), Red Copp 97N Premium (manufactured by AMERICA CHEMET Co.), Purple. Examples include Copp (manufactured by AMERICA CHEMET Co.) and LoLoTint 97 (manufactured by AMERICA CHEMET Co.).
  • an antifouling agent (D) may be used individually by 1 type, and may use 2 or more types together.
  • the total content can be arbitrarily selected from the viewpoint of the effect of the compound used and the availability, but the laminated layer to be formed From the viewpoint of improving the antifouling property and physical properties of the antifouling coating film and reducing the environmental load, it is preferably 0.1 to 90% by mass in the solid content of each antifouling coating composition.
  • the lower layer antifouling coating composition (x) or the upper layer antifouling coating composition (y) contains cuprous oxide or rhodan copper
  • the total content is preferably in the solid content of each coating composition.
  • the total content is preferably in the solid content of each coating composition. 0.5 to 30% by mass, more preferably 1 to 20% by mass.
  • the coating composition of the present invention contains other pigments (E) other than the antifouling agent for the purpose of coloring the coating film and concealing the base, and for the purpose of adjusting to an appropriate coating film strength. Also good.
  • Other pigments (E) include, for example, zinc oxide, talc, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, sulfide.
  • Examples include extender pigments such as zinc, and colored pigments such as petals (red iron oxide), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, and phthalocyanine blue, including zinc oxide and talc. Is preferred. These other pigments may be used alone or in combination of two or more.
  • the coating composition of the present invention contains other pigment (E)
  • the content is determined by the hiding property required for the antifouling coating film to be formed and the viscosity of the antifouling coating composition. However, it is preferably 1 to 60% by mass in the solid content of the coating composition.
  • the coating composition of the present invention may contain a monocarboxylic acid compound (F).
  • the monocarboxylic acid compound (F) improves the renewability of the formed coating film from the surface in water, and when the coating film contains an antifouling agent, It promotes release into water to enhance the antifouling property of the coating film, and also has a function of imparting appropriate water resistance to the coating film.
  • R—COOH R is a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, or 3 carbon atoms. It is preferably a ⁇ 40 saturated or unsaturated alicyclic hydrocarbon group or a substituted product thereof.
  • abietic acid neoabietic acid, dehydroabietic acid, parastrinic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexene carboxylic acid, versatic acid, stearic acid, naphthenic acid and the like are preferable.
  • rosins whose main components are abietic acid, parastrinic acid, isopimaric acid and the like. Examples of rosins include rosins such as gum rosin, wood rosin and tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salts, and pine tar.
  • trimethylisobutenylcyclohexene carboxylic acid examples include a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which is 1,2,3-trimethyl- 5- (2-Methylprop-1-en-1-yl) cyclohex-3-en-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl)
  • the main component 85% by mass or more) of cyclohex-3-ene-1-carboxylic acid.
  • a part or all of the monocarboxylic acid compound (F) in the present invention may form a metal ester.
  • the metal ester include zinc ester and copper ester.
  • the metal ester may be formed in advance before the preparation of the coating composition or may be formed by reaction with other coating components at the time of preparing the coating composition.
  • Monocarboxylic acid compound (F) and / or its metal ester may be used individually by 1 type, and may use 2 or more types together.
  • the content is determined from the viewpoint of coating workability of the coating composition and water resistance of the antifouling coating film.
  • the amount is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass in the solid content of the composition.
  • the coating composition of the present invention may contain a dehydrating agent (G) for the purpose of improving its storage stability.
  • a dehydrating agent (G) examples include synthetic zeolite, anhydrous gypsum (calcium sulfate) and hemihydrate gypsum (also called calcined gypsum) as inorganic dehydrating agents, and tetramethoxysilane and tetraethoxysilane as organic dehydrating agents.
  • a dehydrating agent (G) may be used individually by 1 type, and may use 2 or more types together.
  • the content thereof is preferably 0.1 to 20% by mass in the solid content of the coating composition, more preferably 0.00. The amount is 2 to 15% by mass.
  • the coating composition of the present invention may contain a plasticizer (H) for the purpose of imparting plasticity to the antifouling coating film.
  • a plasticizer (H) examples include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), and the like. These plasticizers may be used alone or in combination of two or more.
  • TCP tricresyl phosphate
  • DOP dioctyl phthalate
  • DIDP diisodecyl phthalate
  • the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition, more preferably 0. The amount is 5 to 5% by mass.
  • the content of the plasticizer (H) is within the above range, the plasticity of the coating film can be kept good.
  • the coating composition of the present invention may contain an anti-sagging agent / anti-settling agent (I) for the purpose of adjusting the viscosity of the coating composition.
  • Anti-sagging agents and anti-settling agents (I) include organic clay waxes (such as Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonates), organic waxes (polyethylene wax, polyethylene oxide wax, amide). Waxes, polyamide waxes, hydrogenated castor oil waxes, etc.), mixtures of organic clay waxes and organic waxes, synthetic finely divided silica and the like.
  • the anti-sagging agent / anti-settling agent (I) Commercially available products may be used as the anti-sagging agent / anti-settling agent (I).
  • Disposaron 305 “Dispalon 4200-20”, “Dispalon A630-20X”, “Dispalon” manufactured by Enomoto Kasei Co., Ltd. 6900-20X ",” ASA D-120 "manufactured by Ito Oil Co., Ltd., and the like.
  • the anti-sagging agent / anti-settling agent (I) may be used alone or in combination of two or more.
  • the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition, The amount is more preferably 0.2 to 3% by mass.
  • the coating composition of the present invention may contain a binder component (J) for the purpose of imparting water resistance, crack resistance and strength to the antifouling coating film to be formed.
  • a binder component (J) for the purpose of imparting water resistance, crack resistance and strength to the antifouling coating film to be formed.
  • the binder component (J) include chlorinated paraffin, n-paraffin, polyester polymer, terpene phenol resin, petroleum resins, and ketone resin. Among these, chlorinated paraffin, polyester polymer, and petroleum resins are preferable.
  • a binder component (J) may be used individually by 1 type, and may use 2 or more types together.
  • the chlorinated paraffin may have a linear or branched molecular structure, and may be liquid or solid (eg, powder) at room temperature (eg, 23 ° C.).
  • the chlorinated paraffin preferably has an average carbon number of 8 to 30 and more preferably 10 to 26 in one molecule.
  • An antifouling coating composition containing such a chlorinated paraffin can form an antifouling coating film with less cracks and peeling.
  • the said average carbon number is less than 8, the effect which suppresses generation
  • the viscosity (unit poise, measurement temperature 25 ° C.) of the chlorinated paraffin is preferably 1 or more, more preferably 1.2 or more, and the specific gravity (25 ° C.) is preferably 1.05 to 1.80 g. / Cm 3 , more preferably 1.10 to 1.70 g / cm 3 .
  • the chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 to 70 parts by mass, preferably 35 to 65 parts by mass when the chlorinated paraffin is 100 parts by mass.
  • a coating composition containing a chlorinated paraffin having such a chlorination rate can form a coating film with few cracks, cracks, and the like.
  • the polyester polymer is obtained by reaction of one or more polyhydric alcohols with one or more polyvalent carboxylic acids and / or anhydrides thereof, and optionally other components, and uses any kind in any amount.
  • the hydroxyl value / acid value and viscosity can be adjusted by the combination.
  • polyhydric alcohol examples include propylene glycol, glycerin, ethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane (TMP), pentaerythritol, sorbitol; polyalkylene glycols such as diethylene glycol; Among them, propylene glycol, ethylene glycol, neopentyl glycol, glycerin, and TMP are preferable because of easy availability of raw materials. These polyhydric alcohols may be used in combination of two or more.
  • polyvalent carboxylic acid and / or anhydride thereof examples include malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,9-nonamethylenedicarboxylic acid.
  • Acid 1,10-decamethylene dicarboxylic acid, 1,11-undecamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, cyclohexane dicarboxylic acid, decahydronaphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, hexa
  • examples include hydrophthalic acid, succinic acid, and the like, and anhydrides thereof, and phthalic anhydride, adipic acid, isophthalic acid, and hexahydrophthalic anhydride are preferable.
  • the polyester polymer preferably has a solid content hydroxyl value of 50 to 150 mgKOH / g, and 80 to 120 mgKOH from the viewpoint of imparting storage stability of the coating composition, antifouling property of the coating film, and appropriate hydrophilicity. / G is more preferable.
  • the polyester polymer may be dissolved in a solvent and used as a solution (hereinafter also referred to as a polyester polymer solution).
  • a solvent those mentioned as the organic solvent (C1) can be used.
  • the viscosity of the polyester polymer solution is preferably 3,000 mPa ⁇ s or less, more preferably 1,000 mPa ⁇ s or less at 25 ° C., from the viewpoint of reducing the viscosity of the coating composition.
  • the polyester polymer solution may contain unreacted raw materials. Examples of the petroleum resins include C5 series, C9 series, styrene series, dichloropentadiene series, and hydrogenated products thereof.
  • the binder component (J) Commercially available products may be used as the binder component (J).
  • the chlorinated paraffin “Toyoparax C-70 / A-50 / A-70 / A-145 / A-150 /” manufactured by Tosoh Corporation may be used.
  • 150 etc.
  • the polyester polymer “ Tesrack 2474 ”manufactured by Hitachi Chemical Co., Ltd.
  • the petroleum resins “ Quinton 1500 ”and“ Quinton 1700 ”(all manufactured by Nippon Zeon Co., Ltd.) And the like.
  • the coating composition of the present invention contains the binder component (J)
  • the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition.
  • the lower-layer antifouling paint composition (x) and the upper-layer antifouling paint composition (y) of the present invention can be prepared using the same devices and means as those of known general paints, respectively. Specifically, in the case of the upper layer antifouling coating composition (y), after preparing the hydrolyzable polymer (A2), the solution of the hydrolyzable polymer (A2) and the organic solvent (C2), and If necessary, other additive components can be added at once or sequentially, and stirred and mixed to produce.
  • the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) may be any of the following aspects (i) to (vii).
  • the lower layer antifouling paint composition (x) or the upper layer antifouling paint composition (y) has a hydrolyzable polymer (A) having a structural unit derived from a silyl ester group-containing monomer. You may contain both the polymer and the hydrolyzable polymer which has a structural unit derived from a metal ester group containing monomer.
  • Both the hydrolyzable polymer (A) contained in the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) are derived from the silyl ester group-containing monomer (a11). It has a structural unit.
  • Both the hydrolyzable polymer (A) contained in the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) are derived from the metal ester group-containing monomer (a12). It has a structural unit.
  • the hydrolyzable polymer (A1) contained in the lower layer antifouling paint composition (x) has a structural unit derived from the metal ester group-containing monomer (a12), and is an upper layer antifouling paint composition
  • the hydrolyzable polymer (A2) contained in (y) has a structural unit derived from the silyl ester group-containing monomer (a11).
  • the lower-layer antifouling paint composition (x) and the upper-layer antifouling paint composition (y) have particularly preferred embodiments described in the following (v) to (vii).
  • the lower layer antifouling coating composition (x) is used as an organic antifouling agent (B1) as 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbohydrate.
  • the hydrolyzable polymer (A2) containing the nitrile and contained in the upper antifouling coating composition (y) has a structural unit derived from the metal ester group-containing monomer (a12).
  • the lower-layer antifouling coating composition (x) contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one as the organic antifouling agent (B1), and the upper-layer antifouling coating
  • the hydrolyzable polymer (A2) contained in the composition (y) has a structural unit derived from the metal ester group-containing monomer (a12).
  • the lower layer antifouling paint composition (x) contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one as the organic antifouling agent (B1), and the upper layer antifouling paint
  • the hydrolyzable polymer (A2) contained in the composition (y) has a structural unit derived from the silyl ester group-containing monomer (a11).
  • the upper antifouling coating composition (y) comprises the organic antifouling agent (B2) and other organic antifouling agents. It is preferable not to contain (B′2) substantially, and it is more preferable not to contain it.
  • the hydrolyzable polymer contained in the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) are both derived from a metal ester group-containing monomer. It is preferable to have a unit (the embodiment (ii) above).
  • the upper layer antifouling coating composition (y) contains the other antifouling agent (D) in addition to the organic antifouling agent (B2) and the other organic antifouling agent (B′2). It is preferable not to contain from a viewpoint of interlayer adhesiveness.
  • the manufacturing method of a base material with a laminated antifouling coating film comprises a step of applying a lower antifouling coating composition (x) on a base material to form a lower antifouling coating film (X), and a lower antifouling coating film (X) It has the process of apply
  • the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) As the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y), the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) described above are used.
  • the applied lower layer antifouling coating composition (x) is dried to form the lower layer antifouling coating film (X).
  • the lower-layer antifouling coating composition (x) applied by the above-described method is dried, for example, by leaving it to stand at 25 ° C., preferably for about 1 hour to 14 days, more preferably about 1 to 7 days.
  • An antifouling coating film (X) can be obtained.
  • the lower layer antifouling paint composition (x) may be dried while blowing air under heating.
  • the thickness of the lower antifouling coating film (X) is arbitrarily selected according to the anticorrosion performance required for the lower antifouling coating film (X), the coating film strength, the period of use, etc., preferably 10 to 1, Although it is about 000 ⁇ m, it is more preferably 50 to 400 ⁇ m, still more preferably 70 to 200 ⁇ m, from the viewpoint of the antifouling property of the laminated antifouling coating film, ease of coating film formation, and resource saving.
  • the lower layer antifouling coating composition (x) is preferably applied at a thickness of 10 to 300 ⁇ m per application, The method of apply
  • the lower layer antifouling paint composition (x) when applied a plurality of times to form the lower layer antifouling coating film (X), two or more layers having different compositions are laminated as the lower layer antifouling paint composition (x). May be.
  • the base material to which the lower layer antifouling paint composition (x) is applied may have a surface on which a coating film such as a primer layer has already been formed, and surface roughening treatment such as sandblasting treatment may be performed.
  • the kind of coating film which the lower layer antifouling coating film (X) is in direct contact with is not particularly limited.
  • an upper antifouling coating composition (y) is applied on the lower antifouling coating film (X) formed on the substrate, and an upper layer is formed. It has the process of forming an antifouling coating film (Y).
  • the method for applying the upper antifouling paint composition (y) is not particularly limited, and can be applied by the same method as the method for applying the lower antifouling paint composition (x) described above.
  • the dirty paint composition (y) can form an upper antifouling coating film (Y) by drying. There are no particular restrictions on the drying conditions of the upper antifouling paint composition (y), but drying under conditions having a period exceeding 0 ° C.
  • the upper layer antifouling coating composition (y) is dried, for example, under conditions of an average temperature of 25 ° C., usually for 1 hour to 14 days, preferably about 1 to 7 days. You may go while doing it.
  • the lower antifouling coating film (X) Prior to the application of the upper antifouling paint composition (y), the lower antifouling coating film (X) may be subjected to a pretreatment such as a roughening treatment with sandpaper or the like, or a surface washing with high-pressure water washing or the like.
  • a pretreatment such as a roughening treatment with sandpaper or the like, or a surface washing with high-pressure water washing or the like.
  • the upper antifouling coating (Y) of the laminated antifouling coating of the present invention is exhausted and exposed to the lower antifouling coating (X), and the antifouling purpose already in the sea
  • an upper antifouling coating composition (y) may be further applied to form a laminated antifouling coating film.
  • the thickness of the upper antifouling coating film (Y) is arbitrarily selected according to the renewal speed of the upper antifouling coating film (Y), the period of use, etc., but is preferably about 40 to 1,500 ⁇ m. From the viewpoint of the antifouling property of the laminated antifouling coating film, the strength of the coating film, and the ease of forming the coating film, it is more preferably 60 to 800 ⁇ m, still more preferably 80 to 600 ⁇ m. As a method for producing a coating film of this thickness, the upper antifouling coating composition (y) is preferably 30 to 500 ⁇ m, more preferably 50 to 200 ⁇ m, once to multiple times per application. The method of apply
  • coating twice is mentioned.
  • the substrate with a laminated antifouling coating film of the present invention is produced by forming the laminated antifouling coating film on the substrate by the method as described above.
  • the laminated antifouling coating film of the present invention can be used for maintaining the antifouling property of a substrate over a long period of time in a wide range of industrial fields such as ships, fisheries, and marine structures.
  • Examples of such base materials include ships (container ships, large steel ships such as tankers, fishing boats, FRP ships, wooden ships, yachts, etc. hull outer plates, new ships or repair ships, etc.), fishing materials (ropes, fishing nets, etc.) , Fishing gear, floats, buoys, etc.) and offshore structures such as mega floats.
  • the base material is preferably selected from the group consisting of ships, underwater structures, and fishing gear, more preferably selected from the group consisting of ships and underwater structures, and is further a ship. preferable.
  • the antifouling method of the present invention uses the above-mentioned laminated antifouling coating film, and is a method of preventing fouling by providing the laminated antifouling coating film of the present invention on various substrates.
  • the coating kit for forming a laminated antifouling coating film of the present invention includes at least the lower antifouling coating composition (x) and the upper antifouling coating composition (y) described above.
  • the coating kit for forming a laminated antifouling coating film of the present invention combines a primer layer forming coating composition and the like in addition to the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y).
  • a kit comprising three or more coating compositions may be used.
  • the upper antifouling coating composition of the present invention is the above-described upper antifouling coating composition (y), which is formed on the lower antifouling coating film (X) formed by the lower antifouling coating composition (x). It is suitably used for forming an upper antifouling coating film (Y).
  • each component used in the examples refers to a component excluding volatile components contained in each component as a solvent, and is obtained by drying each component in a hot air dryer at 125 ° C. for 1 hour. It is a thing.
  • the viscosity of the obtained polymer solutions (A-1) to (A-4) and the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymers contained therein are measured as follows.
  • (Viscosity of polymer solution) The viscosity of the polymer solution at 25 ° C. was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • a pale yellow transparent hydrolyzable polymer solution (A-7) was prepared.
  • Table 2 shows the constitution of the monomer components of the hydrolyzable polymer solutions (A-5) to (A-7) and the characteristic values of the hydrolyzable polymer solutions (A-5) to (A-7). Shown together.
  • the viscosity, number average molecular weight, and weight average molecular weight were measured in the same manner as in the hydrolyzable polymer solution (A-1), and the zinc content (% by mass) was measured using an atomic absorption spectrophotometer (Shimadzu Corporation). Measured by AA6800 (trade name) manufactured by Seisakusho.
  • both tralopyryl and DCOIT are soluble in xylene and propylene glycol monomethyl ether.
  • the solubility of tralopyryl is 1 g / L or more for xylene, 100 g / L or more for propylene glycol monomethyl ether, and DCOIT is 100 g / L or more for both xylene and propylene glycol monomethyl ether.
  • a silicone-based paint composition (trade name “CMP Bioclin HB”, manufactured by China Paint Co., Ltd., does not contain hydrolyzable polymer (A) and organic antifouling agent (B))
  • a coating composition obtained by mixing 3 parts by mass of tralopyril and 10 parts by mass of 2-heptanone with respect to 100 parts by mass of the composition (y-9) was obtained as a lower layer antifouling coating composition (x-8) It was.
  • the lower layer antifouling paint composition (x) produced according to Table 4 was applied once so that the dry film thickness was about 100 ⁇ m
  • the upper antifouling paint composition (y) produced according to Table 5 was applied once so that the dry film thickness was about 200 ⁇ m, and then dried at 25 ° C. for 7 days to obtain a laminated antifouling agent.
  • a test plate with a coating film was prepared. The above three coatings are performed once a day, that is, in the case of repeated coating, after coating the coating composition corresponding to the lower layer coating film, the coating composition is dried at 25 ° C. for at least 24 hours and applied on the coating film. A coating composition corresponding to the upper layer coating film was applied.
  • Example 15 to 17 The lower layer antifouling paint composition (x-6) and the upper layer antifouling agent were prepared in the same manner as in the preparation of Examples 1 to 14 except that each coating composition was changed so that the dry film thickness was as shown in Table 9. A test plate with a laminated antifouling coating film was produced using the coating composition (y-4).
  • a laminated antifouling coating film having a good appearance and capable of exhibiting good antifouling performance and interlayer adhesion, and a basis thereof A base material with a laminated antifouling coating film on the material can be provided.

Abstract

La présente invention concerne un revêtement antisalissure multicouche obtenu par stratification d'un revêtement antisalissure de sous-couche (X) et d'un revêtement antisalissure de couche supérieure (Y), le revêtement antisalissure de sous-couche (X) contenant un polymère hydrolysable (A1) et un agent antisalissure organique (B1), le revêtement antisalissure de couche supérieure (Y) contenant un polymère hydrolysable (A2), et l'agent antisalissure organique (B1) étant un ou plusieurs éléments choisis parmi le 4-bromo-2-(4-chlorophényl)-5-(trifluorométhyl)-1H-pyrrole-3-carbonitrile et la 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one.
PCT/JP2018/020923 2017-06-01 2018-05-31 Revêtement antisalissure multicouche, substrat équipé d'un revêtement antisalissure multicouche et son procédé de production, kit de matériau de revêtement permettant de former un revêtement antisalissure multicouche, composition de matériau de revêtement antisalissure de couche supérieure et procédé antisalissure WO2018221642A1 (fr)

Priority Applications (4)

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KR1020197034774A KR102340452B1 (ko) 2017-06-01 2018-05-31 적층 방오 도막, 적층 방오 도막 부착 기재 및 그의 제조 방법, 적층 방오 도막 형성용 도료 키트, 상층 방오 도료 조성물, 및 방오 방법
JP2019521294A JP6948391B2 (ja) 2017-06-01 2018-05-31 積層防汚塗膜、積層防汚塗膜付き基材及びその製造方法、積層防汚塗膜形成用塗料キット、上層防汚塗料組成物、並びに防汚方法
SG11201911459UA SG11201911459UA (en) 2017-06-01 2018-05-31 Multilayer antifouling coating film, substrate with multilayer antifouling coating film and method for producing same, coating material kit for forming multilayer antifouling coating film, upper-layer antifouling coating composition, and antifouling method
CN201880035121.6A CN110709484A (zh) 2017-06-01 2018-05-31 层叠防污涂膜、带层叠防污涂膜的基材及其制造方法、层叠防污涂膜形成用涂料套件、上层防污涂料组合物和防污方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020152807A (ja) * 2019-03-20 2020-09-24 関西ペイント株式会社 防汚塗料組成物
JP2020189447A (ja) * 2019-05-22 2020-11-26 日東化成株式会社 複層防汚塗膜、該塗膜を表面に有する塗装物
WO2022102493A1 (fr) * 2020-11-10 2022-05-19 日東化成株式会社 Copolymère pour composition de peinture antisalissure, et composition de peinture antisalissure

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