WO2018221641A1 - Revêtement antisalissures multicouche, substrat équipé d'un revêtement antisalissures multicouche et son procédé de production, kit de matériau de revêtement pour former un revêtement antisalissures multicouche, composition de matériau de revêtement antisalissures de couche supérieure et procédé antisalissures - Google Patents

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

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Publication number
WO2018221641A1
WO2018221641A1 PCT/JP2018/020920 JP2018020920W WO2018221641A1 WO 2018221641 A1 WO2018221641 A1 WO 2018221641A1 JP 2018020920 W JP2018020920 W JP 2018020920W WO 2018221641 A1 WO2018221641 A1 WO 2018221641A1
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WO
WIPO (PCT)
Prior art keywords
antifouling
antifouling coating
coating film
polymer
organic
Prior art date
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PCT/JP2018/020920
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English (en)
Japanese (ja)
Inventor
聡一郎 谷野
Original Assignee
中国塗料株式会社
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 中国塗料株式会社 filed Critical 中国塗料株式会社
Priority to JP2019521293A priority Critical patent/JP6948390B2/ja
Priority to KR1020197034772A priority patent/KR102340449B1/ko
Priority to CN201880035177.1A priority patent/CN110691826A/zh
Publication of WO2018221641A1 publication Critical patent/WO2018221641A1/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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • C09D5/1693—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
    • 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 present invention relates to the following [1] to [18].
  • [1] A laminated antifouling coating film in which a lower antifouling coating film (X) and an upper antifouling coating film (Y) are laminated.
  • the lower antifouling coating film (X) is a polymer (B1).
  • an organic antifouling agent (C1), and the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond
  • the upper antifouling coating film (Y) is a laminated antifouling coating film containing a hydrolyzable polymer (A2).
  • 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) includes 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):
  • the antifouling coating film according to [6] which contains at least one of
  • 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 lower antifouling coating film (X) is used as the organic antifouling agent (C1) as 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbohydrate.
  • the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond, and the upper antifouling paint composition (y) is hydrolyzable.
  • the organic solvent (D2) contains one or more selected from the group consisting of hydrocarbon solvents, alcohol solvents, ketone solvents, and ester solvents.
  • the upper antifouling coating composition (y) contains an organic antifouling agent (C2), and the content (mass%) of the organic antifouling agent (C2) in the upper antifouling coating composition (y).
  • the antifouling paint according to any one of [12] to [14], which is lower than the content (% by mass) of the organic antifouling agent (C1) in the lower layer antifouling coating composition (x) The manufacturing method of a base material with a film. [16] The laminated antifouling coating film according to any one of [12] to [15], wherein the upper antifouling coating composition (y) contains substantially no organic antifouling agent (C2) A method for producing a substrate.
  • Lower layer antifouling paint composition (x) containing polymer (B1) and organic antifouling agent (C1), and upper layer containing hydrolyzable polymer (A2) and organic solvent (D2)
  • a coating kit for forming a laminated antifouling coating film comprising an antifouling coating composition (y), wherein the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond.
  • 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 polymer (B1) and an organic antifouling agent (C1), and the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond.
  • the upper antifouling coating film (Y) contains a hydrolyzable polymer (A2).
  • 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. Furthermore, the manufacturing method of the base material with a lamination
  • 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 present inventors have found that high antifouling performance is exhibited over a long period of time even under conditions where the fouling load is high and the present invention has been completed.
  • the detailed mechanism of action for obtaining the above effect is not necessarily clear, a part is estimated as follows. That is, the organic antifouling agent (C1) contained in the lower antifouling coating film (X) was unevenly distributed near 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 (C1) as a whole laminated antifouling coating film is brought close to the surface.
  • the organic antifouling agent (C1) is continuously supplied from the lower antifouling coating film (X) in the upper antifouling coating film (Y), the initial stage Therefore, it is estimated that high antifouling performance can be exhibited over a long period of time.
  • the upper layer antifouling coating film (Y) contains the hydrolyzable polymer (A2), the antifouling property is exhibited also by the coating film renewability of the upper layer antifouling coating film (Y).
  • the upper antifouling coating composition (y) for forming the upper antifouling coating film (Y) contains the organic solvent (D2), and the organic solvent (D2) is the lower antifouling coating film (X).
  • the polymer (B1) and the organic antifouling agent (C1) contained in Since the organic antifouling agent (C1) is extracted in the coating composition (y) and an appropriate amount of the organic antifouling agent (C) is supplied into the upper antifouling coating film (Y), it is high from the beginning. It is estimated that antifouling performance can be exhibited.
  • 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 (C1) 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 (C1) 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 layer antifouling coating film (X) contains a polymer (B1) and an organic antifouling agent (C1).
  • the lower layer antifouling coating film (X) may further contain a hydrolyzable polymer (A1).
  • the lower layer antifouling coating composition (x) suitably used for forming the lower layer antifouling coating film (X) contains the polymer (B1) and the organic antifouling agent (C1), and further contains an organic solvent. It is preferable to contain (D1). Moreover, in addition to the said component, you may contain a hydrolysable polymer (A1).
  • 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 (D2) in addition to the hydrolyzable polymer (A2). preferable.
  • each component used for an antifouling coating film and an antifouling coating composition is demonstrated.
  • the upper antifouling coating film (Y) may contain a hydrolyzable polymer (A2)
  • the lower antifouling coating film (X) may contain a hydrolyzable polymer (A1).
  • the hydrolyzable polymer (A1) and the hydrolyzable polymer (A2) are collectively referred to as a hydrolyzable polymer (A).
  • the upper antifouling coating film (Y) contains the hydrolyzable polymer (A2)
  • the upper antifouling coating film (Y) is given antifouling properties due to appropriate water resistance and coating film renewability.
  • the lower layer antifouling coating film (X) contains the hydrolyzable polymer (A1)
  • appropriate water resistance and coating film renewability are imparted to the lower layer antifouling coating film (X).
  • 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 upper layer antifouling paint composition (y) contains the hydrolyzable polymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11).
  • the upper layer antifouling coating composition (y) contains a hydrolyzable polymer (A2) having a structural unit derived from the metal ester group-containing monomer (a12). This is preferable from the viewpoint of improving the antifouling property of the film and the physical 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 product 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) when the hydrolyzable polymer (A) has a structural unit derived from the polyorganosiloxane block-containing monomer (a21), the slime resistance, which is estimated to be due to the contribution of the polyorganosiloxane block, is increased. 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 layer antifouling coating film (X) and the lower layer antifouling coating composition (x) contain a polymer (B1).
  • the lower layer antifouling coating film (X) and the lower layer antifouling coating composition (x) may contain the hydrolyzable polymer (A1) described above in addition to the polymer (B1).
  • a polymer (B1) is a polymer which has a structural unit derived from the monomer which has an unsaturated double bond, and is a polymer except the hydrolyzable polymer (A) mentioned above.
  • the polymer having a structural unit does not correspond to the polymer (B1). That is, the polymer (B1) does not contain a structural unit derived from the hydrolyzable group-containing monomer (a1).
  • the polymer (B1) is preferably soluble in the organic solvent (D2) contained in the upper antifouling coating composition (y).
  • “soluble” means that the solubility at 23 ° C. is 1 g / L or more. More preferably, the polymer (B1) has a solubility in the organic solvent (D2) at 23 ° C. of 10 g / L or more.
  • the organic antifouling agent (C1) can be efficiently supplied to the upper antifouling coating film (Y) formed from the upper antifouling coating composition (y). Moreover, the interlayer adhesion between the upper antifouling coating film (Y) and the lower antifouling coating film (X) can be improved.
  • the polymer (B1) is preferably a thermoplastic resin.
  • the polymer (B1) is a thermoplastic resin, good adhesion to the substrate is obtained, and good solubility in the organic solvent (D2) contained in the upper antifouling coating composition (y) is obtained. Easy to obtain.
  • Specific examples of such a polymer (B1) include chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene; (meth) methyl acrylate copolymers, (meth) ethyl acrylate copolymers.
  • Acrylic resins such as polymers, (meth) propyl acrylate copolymers, (meth) butyl acrylate copolymers, (meth) cyclohexyl cyclohexyl copolymers; vinyl chloride-vinyl acetate copolymers, Vinyl chloride resins (vinyl chloride copolymer) such as vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, vinyl chloride-ethyl vinyl ether copolymer; styrene Aromatic petroleum resin; Aliphatic petroleum resin; Urea aldehyde condensation resin; Ketone resin It can gel.
  • the polymer (B1) preferably contains a structural unit derived from vinyl chloride from the viewpoints of adhesion of the lower antifouling coating film (X) to the substrate and excellent coating properties. Moreover, in addition to the structural unit derived from vinyl chloride, you may have the structural unit derived from vinyl acetate, the structural unit derived from vinyl alcohol, and the structural unit derived from alkyl vinyl ether (for example, isobutyl vinyl ether etc.). Furthermore, as another preferable aspect of the polymer (B1), a homopolymer or copolymer (hereinafter also referred to as (meth) acrylic polymer) of (meth) acrylic acid and / or (meth) acrylic acid ester. ).
  • the polymer (B1) may be used singly or in combination of two or more.
  • the polymer having a structural unit derived from vinyl chloride described above The combined use of a (meth) acrylic polymer is mentioned.
  • the weight average molecular weight of the polymer (B1) is preferably in the range of 5,000 to 100,000.
  • a commercially available product can be used.
  • “Laroflex MP25” (a copolymer of vinyl chloride and isobutyl vinyl ether) manufactured by BASF, Nissin Chemical Industry Co., Ltd.
  • “Solvine C” (copolymer of vinyl chloride and vinyl acetate)
  • “Solvain AL” copolymer of vinyl chloride, vinyl acetate, and vinyl alcohol
  • “Dianal BR-106” manufactured by Mitsubishi Rayon Co., Ltd. (Acrylic copolymer (acrylic resin)) and the like.
  • the amount of the polymer (B1) in the lower layer antifouling coating film (X), from the viewpoint of the antifouling property and physical properties of the laminated antifouling coating film is preferably 5 to 90% by mass, more preferably 10 to 50% by mass. Further, the total content (total content) of the polymer (B1) and the hydrolyzable polymer (A1) in the solid content of the lower layer antifouling coating composition (x), that is, the lower layer antifouling coating film (X).
  • the upper antifouling coating composition (y) may optionally contain the polymer (B2), but preferably does not contain the polymer (B2) from the viewpoint of coating film renewability.
  • the lower antifouling coating film (X) and the lower antifouling coating composition (x) contain an organic antifouling agent (C1).
  • an organic antifouling agent (C1) is a compound which has antifouling property and does not contain a metal element. Note that boron, which is a semimetal, does not correspond to a metal element.
  • organic antifouling agent (C1) examples include 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as tralopyryl), 4,5 -Borane-nitrogen base adducts such as dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT), pyridinetriphenylborane, 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-trichlorophenyl) maleimide, 2,4,5,6-tetrachloroisophthalonitrile,
  • the organic antifouling agent (C1) is soluble in the organic solvent (D2) described later contained in the upper antifouling coating composition (y), that is, the solubility at 23 ° C. is 1 g /
  • the organic antifouling agent (C1) preferably has a solubility in an organic solvent (D2) at 23 ° C. of 10 g / L or more, and more preferably 100 g / L or more.
  • the organic antifouling agent (C1) preferably contains at least one selected from tralopyril and DCOIT from the viewpoint of imparting excellent antifouling properties to the laminated antifouling coating film, and is particularly antifouling against barnacle species. It is more preferable to contain tralopyril from the viewpoint of improving the odor, and it is preferable to include DCOIT from the viewpoint of improving the antifouling property against slime, which is a cell secretion.
  • An organic antifouling agent (C1) may be used individually by 1 type, and may use 2 or more types together.
  • the total content of the organic antifouling agent (C1) in the lower layer antifouling paint composition (x) can be arbitrarily selected according to the efficacy and cost of the compound used, but the antifouling property excellent in the laminated antifouling coating film.
  • the solid content of the lower layer antifouling coating composition (x) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 3 to 20% by mass. It is.
  • the content of the organic antifouling agent (C1) 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. Fluctuates with dissolution in solvent (D2) and supply of organic antifouling agent (C1) from lower antifouling coating (X) to upper antifouling coating (Y) in the laminated antifouling coating . Therefore, it is most appropriate to define the content of the organic antifouling agent (C1) by the content in the solid content of the lower layer antifouling coating composition (x).
  • the lower layer antifouling paint composition (x) contains tralopyril as the organic antifouling agent (C1), from the viewpoint of improving the antifouling properties and coating film properties of the laminated antifouling coating film and interlayer adhesion,
  • the content of is preferably 1 to 30% by mass, more preferably 3 to 20% by mass in the solid content of the lower layer antifouling coating composition (x).
  • the lower layer antifouling paint composition (x) contains DCOIT as the organic antifouling agent (C1), from the same viewpoint, the content of DCOIT is determined based on the solid content of the lower layer antifouling paint composition (x).
  • the content is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass, and still more preferably 2 to 10% by mass.
  • the upper antifouling coating composition (y) may optionally contain an organic antifouling agent (C2) as long as it does not hinder the problem to be solved by the present invention.
  • the upper antifouling coating composition (y) contains the organic antifouling agent (C2), the antifouling performance of the laminated antifouling coating film can be further improved.
  • the upper layer antifouling paint composition (y) contains the organic antifouling agent (C2), the above-mentioned ones can be used.
  • the upper layer antifouling paint composition (y) The organic antifouling agent (C2) content of the organic antifouling agent (C2) in the upper antifouling coating (Y) is the same as the organic antifouling agent (X) in the lower antifouling coating (X). It is preferable that the amount is lower than the content of C). Moreover, when the upper-layer antifouling paint composition (y) contains an organic antifouling agent (C2), from the viewpoint of preventing precipitates from forming on the surface of the antifouling coating film, the organic antifouling agent (C2 as described above) is used.
  • the coating composition does not substantially contain the object means that the concentration of the object in the solid content of the coating composition is less than 0.1% by mass, preferably It is 0.05 mass% or less, More preferably, it is 0.03 mass% or less, More preferably, it is 0.01 mass% or less.
  • the upper-layer antifouling coating composition (y) contains the hydrolyzable copolymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11)
  • the hydrolyzable copolymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11)
  • Combined use of borane-nitrogen base adducts such as phenylborane and 4-isopropylpyridinediphenylmethylborane and nitrogen-containing heterocyclic organic antifouling agents such as medetomidine may cause problems such as thickening of coating compositions over time. Therefore, it is particularly preferable that these are not substantially contained.
  • the content thereof is preferably 0.1% by mass to 10% in the solid content of the upper layer antifouling paint composition (y). % By mass, more preferably 0.3% by mass to 5% by mass.
  • the upper antifouling coating composition (y) is obtained by extracting the organic antifouling agent (C1) 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 (D2) for the purpose of adjusting.
  • the upper antifouling paint composition (y) may contain the solvent used when preparing the hydrolyzable polymer (A2) as the organic solvent (D2). When mixing A2) and other components as necessary, a separately added solvent may be contained. In this invention, it is preferable to select what the organic antifouling agent (C1) and polymer (B1) mentioned above are soluble as an organic solvent (D2).
  • soluble means that the solubility at 23 ° C. is 1 g / L or more.
  • the organic solvent (D2) preferably contains an organic antifouling agent (C1) having a solubility at 23 ° C. of 10 g / L or more, more preferably 100 g / L or more.
  • C1 organic antifouling agent having a solubility at 23 ° C. of 10 g / L or more, more preferably 100 g / L or more.
  • an organic solvent (D2) it is preferable that the thing in which the solubility in 23 degreeC of a polymer (B1) is 10 g / L or more is included, and it is more preferable that what is 100 g / L or more is included.
  • the solubility can be determined, for example, by the following method.
  • the concentration of the medium in the supernatant can be determined by measuring with a measuring method such as HPLC.
  • the solubility is 100 g / L or more.
  • Organic solvents (D2) 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 antifouling agent (C1) contained in the lower antifouling coating (X) to the upper antifouling coating (Y) is used.
  • the above-mentioned ester organic solvent or ketone organic solvent is preferably contained, and an ester organic solvent is more preferably contained.
  • the upper layer antifouling paint composition (y) contains an ester organic solvent or a ketone organic solvent as the organic solvent (D2), the content thereof is 1 to 50 in the upper layer antifouling paint composition (y).
  • the mass is preferably 2, and more preferably 2 to 30% by mass.
  • the organic antifouling agent (C1) 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 (D2) may be used individually by 1 type, and may use 2 or more types together.
  • the organic solvent (D2) contained in the upper antifouling coating composition (y) is an organic antifouling agent (C1) contained in the lower antifouling coating film (X) and the lower antifouling coating composition (x). ) Is preferably soluble.
  • the organic solvent (D2) is soluble in the organic antifouling agent (C1).
  • the organic solvent (D2) 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 (D2) 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 viewpoint of supplying the organic antifouling agent (C1) 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 paint composition (x) may also contain an organic solvent (D1).
  • the organic solvent (D1) are the same as the organic solvent (D2) contained in the upper antifouling coating composition (y).
  • the content of the organic solvent (D1) in the lower layer antifouling coating 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 (E) for the purpose of further improving the antifouling property of the coating film to be formed.
  • the other antifouling agent (E) is an antifouling agent other than the organic antifouling agent (C), and contains a metal element.
  • the organic antifouling agent (C) and the other antifouling agent (E) are also collectively referred to 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 (C1) derived from the lower antifouling coating film (X).
  • the coating composition (y) contains the other antifouling agent (E)
  • 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 the other antifouling agent (E)
  • the coating film exhibits good antifouling properties in a situation where the coating film needs antifouling properties.
  • antifouling agents (E) 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.).
  • antifouling agent (E) may be used individually by 1 type, and may use 2 or more types together.
  • the total content thereof can be arbitrarily selected from the viewpoint of the effect of the compound used and the availability, but the laminate 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 (F) 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 (F) 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 (F) may be used alone or in combination of two or more.
  • the coating composition of the present invention contains other pigment (F)
  • 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 (G).
  • the monocarboxylic acid compound (G) 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.
  • the monocarboxylic acid compound (G) include, when the monocarboxylic acid compound is represented by 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 (G) 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 (G) 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 (H) for the purpose of improving its storage stability.
  • a dehydrating agent (H) 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 (H) 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 (I) for the purpose of imparting plasticity to the antifouling coating film.
  • a plasticizer (I) for the purpose of imparting plasticity to the antifouling coating film.
  • the plasticizer (I) include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), and the like. These plasticizers may be used alone or in combination of two or more.
  • the coating composition of the present invention contains the plasticizer (I)
  • 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 10% by mass.
  • the content of the plasticizer (I) 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 (J) for the purpose of adjusting the viscosity of the coating composition.
  • Anti-sagging agents and anti-settling agents (J) 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.
  • J anti-sagging agent / anti-settling agent
  • DISPARON 305 Commercially available products may be used as the anti-sagging agent / anti-settling agent (J), such as “DISPARON 305”, “DISPARON 4200-20”, “DISPARON A630-20X”, “DISPARON” 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 (J) 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, More preferably, the amount is 0.2 to 5% by mass.
  • the coating composition of the present invention may contain a binder component (K) for the purpose of imparting water resistance, crack resistance and strength to the antifouling coating film to be formed.
  • a binder component (K) for the purpose of imparting water resistance, crack resistance and strength to the antifouling coating film to be formed.
  • the binder component (K) include chlorinated paraffins, n-paraffins, polyester polymers, terpene phenol resins, petroleum resins, and ketone resins. Among these, chlorinated paraffin, polyester polymer, and petroleum resins are preferable.
  • a binder component (K) 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 (D2) 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 (K) Commercially available products may be used as the binder component (K).
  • the chlorinated paraffin Toyoparax C-70 / A-50 / A-70 / A-145 / A-150 / manufactured by Tosoh Corporation 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 (K)
  • the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition.
  • the coating composition of the present invention may contain an epoxy resin (L).
  • the epoxy resin (L) is a reactive curable resin that has two or more epoxy groups in one molecule and can be cured by reaction with a curing agent.
  • the epoxy resin (L) also functions as a stabilizer by trapping chlorine when the vinyl chloride polymer is contained as the polymer (B1) in the lower layer antifouling paint composition (x).
  • Examples of the epoxy resin (L) include a bisphenol type, a novolac type, and an aliphatic type, and a bisphenol type epoxy resin is preferable from the viewpoint of workability and rust prevention.
  • the bisphenol type epoxy resin preferably has an epoxy equivalent of 160 to 500, and more preferably 180 to 500.
  • bisphenol type epoxy resins examples include bisphenol A type and bisphenol F type epoxy resins, dimer acid-modified and polysulfide-modified bisphenol type epoxy resins, and hydrogenated products of these bisphenol type epoxy resins.
  • bisphenol A type epoxy resins are preferable.
  • the bisphenol A type epoxy resin examples include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A propylene oxide diglycidyl ether.
  • the bisphenol A type diglycidyl ether examples include bisphenol F type diglycidyl ether such as bisphenol F diglycidyl ether.
  • the lower layer antifouling paint composition (x) contains the epoxy resin (L)
  • the content thereof is the antifouling property, anticorrosive property, curability, coating film physical property, etc. of the laminated antifouling coating film.
  • the solid content of the lower layer antifouling coating composition (x) is preferably 1 to 60% by mass, and more preferably 3 to 50% by mass.
  • the epoxy resin (L) is not practically contained from the viewpoint of improving the antifouling property.
  • the upper-layer antifouling coating composition (y) of the present invention may also contain an epoxy resin (L), but is preferably not substantially contained from the viewpoint of antifouling properties and renewability of the coating film.
  • the coating composition of the present invention may contain an epoxy resin curing agent (M), and when the coating composition contains the epoxy resin (L). It is preferable to contain the epoxy resin curing agent (M).
  • the coating composition contains both the epoxy resin (L) and the epoxy resin curing agent (M)
  • the epoxy resin (L) and the epoxy resin curing agent (M) are cured to form a coating film. Good coating film physical properties and adhesion to the substrate can be imparted.
  • the coating composition contains both the epoxy resin (L) and the epoxy resin curing agent (M)
  • the coating composition is preferably prepared as a multi-component kit containing them in different components. It is preferable to use the composition after mixing immediately before use.
  • Examples of the epoxy resin curing agent (M) include amine-based curing agents, mercapto-based curing agents, acid anhydride-based curing agents, etc., which have good reactivity at room temperature and are easy to handle.
  • a curing agent is usually used.
  • Examples of the amine curing agent include bifunctional or higher amines such as aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines, and modified products thereof.
  • Examples of the aliphatic amine include diethylenetriamine, dipropylenetriamine, tetraethylenepentamine, bis (cyanoethyl) diethylenetriamine, bishexamethylenetriamine, and m-xylylenediamine (MXDA).
  • Examples of the alicyclic amines include 4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, norbornanediamine (NBDA / 2,5- and 2,6-bis (aminomethyl) -bicyclo [2,2, 1) heptane), isophoronediamine (IPDA / 3-aminomethyl-3,5,5-trimethylcyclohexylamine) and the like.
  • Examples of the aromatic amine include phenylenediamine, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, and the like.
  • Examples of the heterocyclic amine include N-methylpiperazine.
  • modified amines include polyamides of amines and modified products thereof, epoxy adducts to which an epoxy compound is added, Mannich modified products, and the like, and epoxy adducts from the viewpoint of curability of coating compositions.
  • Polyamide and modified products thereof are preferable in terms of corrosion resistance and adhesion.
  • the active hydrogen equivalent of such an amine curing agent is preferably 40 to 1,000 g / eq, more preferably 80 to 600 g / eq, from the viewpoint of the balance between curability and adhesion of the coating composition.
  • Specific examples of the amine curing agent include polyamides such as “RACAMIDE N-153”, “RACAMIDE TD-966” manufactured by DIC Corporation, and “SANMIDE 315” manufactured by Sanwa Chemical Industry Co., Ltd.
  • PA-23 manufactured by Akira Otake Shin Chemical Co., Ltd., which is an epoxy adduct obtained by adding an epoxy compound to polyamide, “ADEKA” manufactured by ADEKA, a modified Mannich product of modified polyamide.
  • Hardener EH-350 "and the like.
  • epoxy resin curing agents (M) may be used singly or in combination of two or more.
  • the coating composition contains an epoxy resin (L) and a curing agent for epoxy resin (M), and an amine curing agent is used as the curing agent for epoxy resin (M)
  • the epoxy resin (L) has an epoxy.
  • An amount such that the equivalent ratio of the component to the amine component (epoxy equivalent: active hydrogen equivalent) is preferably 1: 0.25 to 1: 0.9, more preferably 1: 0.3 to 1: 0.8 It is preferable to use in.
  • the curing agent for epoxy resin (M) is used in such an amount, there is a tendency that a coating film excellent in drying property, corrosion resistance, and upper layer compatibility can be obtained.
  • the curing agent for epoxy resin (M) is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the epoxy resin in the coating composition. Used in the amount of.
  • the upper layer antifouling paint composition (y) of the present invention may also contain an epoxy resin curing agent (M), but it is preferably not substantially contained from the viewpoint of the antifouling property of the coating film.
  • the coating composition of the present invention may contain an epoxy resin curing accelerator (N), and the coating composition is used for the epoxy resin (L) and the epoxy resin.
  • the curing agent (M) it is preferable that the curing accelerator for epoxy resin (N) is contained because the coating film exhibits good curability even at a low temperature.
  • the epoxy resin curing accelerator (N) includes tertiary amine compounds such as tri (dimethylaminomethyl) phenol (TAP), diazabicycloundecene (DBU), diazabicyclononene (DBN); 2-ethyl- Examples include imidazole compounds such as 4-methylimidazole; compounds such as phosphine and phosphonium salt compounds. Among them, tertiary amine compounds are preferable and TAP is more preferable from the viewpoint of reaction acceleration and availability.
  • the epoxy resin curing accelerator (N) is 100 masses of the epoxy resin curing agent (M).
  • the upper-layer antifouling coating composition (y) of the present invention may also contain an epoxy resin curing accelerator (N), but is preferably not substantially contained from the viewpoint of the antifouling property of the coating film.
  • 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 (D2), 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 (viii).
  • 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.
  • the lower layer antifouling coating composition (x) does not contain a hydrolyzable polymer (A1).
  • the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) contain a hydrolyzable polymer (A), and both the hydrolyzable polymer (A) are silyl It has a structural unit derived from the ester group-containing monomer (a11).
  • the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) contain a hydrolyzable polymer (A), and both the hydrolyzable polymer (A) are metal It has a structural unit derived from the ester group-containing monomer (a12).
  • the lower layer antifouling coating composition (x) contains the hydrolyzable polymer (A1), and the hydrolyzable polymer (A1) is derived from the silyl ester group-containing monomer (a11).
  • the hydrolyzable polymer (A2) having a structural unit and contained in the upper antifouling paint composition (y) has a structural unit derived from the metal ester group-containing monomer (a12).
  • the lower layer antifouling coating composition (x) contains the hydrolyzable polymer (A1), and the hydrolyzable polymer (A1) is derived from the metal ester group-containing monomer (a12).
  • the hydrolyzable polymer (A2) having a structural unit and contained in the upper antifouling paint composition (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 (vi) to (viii).
  • the lower layer antifouling coating composition (x) is used as an organic antifouling agent (C1) 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 paint composition (x) contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one as the organic antifouling agent (C1), and the upper-layer antifouling paint
  • 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 (C1), 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) substantially contains the organic antifouling agent (C2). It is preferable not to contain, and it is more preferable not to contain.
  • 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 and / or cured to form the lower layer antifouling coating film (X).
  • the lower layer antifouling coating composition (x) applied by the above-mentioned method is dried and / or left by standing, for example, at 25 ° C., preferably for about 1 hour to 14 days, more preferably for about 1 to 7 days. It hardens
  • the lower layer antifouling paint composition (x) may be dried and / or cured while blowing with 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.).
  • ⁇ Production Example 7 Production of hydrolyzable polymer solution (A-7)> Into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe, and a heating / cooling jacket, 10.0 parts of PGM, 63.0 parts of xylene, and 3.0 parts of ethyl acrylate were charged and stirred. The temperature was raised to 100 ⁇ 5 ° C.
  • a pale yellow transparent hydrolyzable polymer solution (A-8) was prepared.
  • Table 2 shows the constitution of the monomer components of the hydrolyzable polymer solutions (A-5) to (A-8) and the characteristic values of the hydrolyzable polymer solutions (A-5) to (A-8). 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.
  • the organic antifouling agent (C) used is 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, DCOIT is 100 g / L or more for all, and PK is 1 g / L or more for all.
  • Medetomidine is 1 g / L or more with respect to xylene, and 100 g / L or more with respect to propylene glycol monomethyl-ter.
  • all the used polymers (B) are soluble in the organic solvent mixed liquid of the ratio described in the Example, The solubility is 100 g / L or more.
  • 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-12) was obtained as a lower layer antifouling coating composition (x-20). 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.
  • a laminated antifouling coating film having a good appearance and capable of exhibiting antifouling performance and interlayer adhesion, and this on a substrate A substrate with a laminated antifouling coating film can be provided.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un revêtement antisalissures multicouche obtenu par stratification d'un revêtement antisalissures de sous-couche (X) et d'un revêtement antisalissures de couche supérieure (Y), le revêtement antisalissures de sous-couche (X) contenant un polymère (B1) et un agent antisalissures organique (C1), le polymère (B1) étant un polymère ayant une unité constitutive dérivée d'un monomère ayant une double liaison insaturée et le revêtement antisalissures de couche supérieure (Y) contenant un polymère hydrolysable (A2).
PCT/JP2018/020920 2017-06-01 2018-05-31 Revêtement antisalissures multicouche, substrat équipé d'un revêtement antisalissures multicouche et son procédé de production, kit de matériau de revêtement pour former un revêtement antisalissures multicouche, composition de matériau de revêtement antisalissures de couche supérieure et procédé antisalissures WO2018221641A1 (fr)

Priority Applications (3)

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JP2019521293A JP6948390B2 (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
KR1020197034772A KR102340449B1 (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
CN201880035177.1A CN110691826A (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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JP2017-109481 2017-06-01
JP2017109481 2017-06-01

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WO2021182454A1 (fr) * 2020-03-13 2021-09-16 中国塗料株式会社 Composition de revêtement antisalissure

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JPS59159862A (ja) * 1983-02-28 1984-09-10 Nippon Paint Co Ltd 船体外板防汚方法
JPH0253874A (ja) * 1988-08-18 1990-02-22 Sumitomo Metal Ind Ltd 防汚被覆方法
JPH11263937A (ja) * 1998-03-19 1999-09-28 Nof Corp 複層塗膜および防汚方法
JP2002256176A (ja) * 2001-02-27 2002-09-11 Chugoku Marine Paints Ltd 複合防汚塗膜、該塗膜で被覆された船舶、水中構造物、漁具または漁網および防汚方法
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WO2011046087A1 (fr) * 2009-10-13 2011-04-21 日本ペイントマリン株式会社 Composition de revêtement antisalissure, film antisalissure, film composite et structure immergée dans l'eau
JP2012005934A (ja) * 2010-06-23 2012-01-12 Nippon Paint Marine Kk 防汚塗膜の形成方法
JP2016502574A (ja) * 2012-11-06 2016-01-28 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 防汚塗料系

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EP0762955A4 (fr) 1994-05-31 1998-01-07 Us Health Revetements maritimes antisalissure
SG185477A1 (en) 2010-06-17 2013-01-30 Nippon Paint Marine Coatings Co Ltd Antifouling paint composition, antifouling coating film, and method for controlling hydrolysis rate of antifouling coating film

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JPS59159862A (ja) * 1983-02-28 1984-09-10 Nippon Paint Co Ltd 船体外板防汚方法
JPH0253874A (ja) * 1988-08-18 1990-02-22 Sumitomo Metal Ind Ltd 防汚被覆方法
JPH11263937A (ja) * 1998-03-19 1999-09-28 Nof Corp 複層塗膜および防汚方法
JP2002256176A (ja) * 2001-02-27 2002-09-11 Chugoku Marine Paints Ltd 複合防汚塗膜、該塗膜で被覆された船舶、水中構造物、漁具または漁網および防汚方法
WO2007026692A1 (fr) * 2005-09-01 2007-03-08 Chugoku Marine Paints, Ltd. Composition de revêtement antitache, film de revêtement antitache, substrat ayant un film de revêtement, substrat antitache, procédé de formation d'un film de revêtement sur la surface du substrat et procédé d’imperméabilisation aux taches du substrat
JP2007246527A (ja) * 2006-03-16 2007-09-27 Rohm & Haas Co カプセル化殺生物剤のブレンド
JP2010150355A (ja) * 2008-12-25 2010-07-08 Nippon Paint Marine Kk 防汚塗料組成物、防汚塗膜、ならびに防汚塗膜の加水分解速度の制御方法
WO2011046087A1 (fr) * 2009-10-13 2011-04-21 日本ペイントマリン株式会社 Composition de revêtement antisalissure, film antisalissure, film composite et structure immergée dans l'eau
JP2012005934A (ja) * 2010-06-23 2012-01-12 Nippon Paint Marine Kk 防汚塗膜の形成方法
JP2016502574A (ja) * 2012-11-06 2016-01-28 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 防汚塗料系

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021182454A1 (fr) * 2020-03-13 2021-09-16 中国塗料株式会社 Composition de revêtement antisalissure
JP6976495B1 (ja) * 2020-03-13 2021-12-08 中国塗料株式会社 防汚塗料組成物

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KR102340449B9 (ko) 2023-06-02
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JP6948390B2 (ja) 2021-10-13
KR20200003000A (ko) 2020-01-08

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