[go: up one dir, main page]

WO2017130864A1 - Composition de revêtement antisalissure, film de revêtement, et matériau de base fixé à un film de revêtement - Google Patents

Composition de revêtement antisalissure, film de revêtement, et matériau de base fixé à un film de revêtement Download PDF

Info

Publication number
WO2017130864A1
WO2017130864A1 PCT/JP2017/001967 JP2017001967W WO2017130864A1 WO 2017130864 A1 WO2017130864 A1 WO 2017130864A1 JP 2017001967 W JP2017001967 W JP 2017001967W WO 2017130864 A1 WO2017130864 A1 WO 2017130864A1
Authority
WO
WIPO (PCT)
Prior art keywords
antifouling
coating film
meth
mass
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/001967
Other languages
English (en)
Japanese (ja)
Inventor
順治 仁井本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chugoku Marine Paints Ltd
Original Assignee
Chugoku Marine Paints Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=59398012&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2017130864(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Chugoku Marine Paints Ltd filed Critical Chugoku Marine Paints Ltd
Priority to CN201780007934.XA priority Critical patent/CN108603069A/zh
Priority to JP2017564214A priority patent/JP6737456B2/ja
Priority to SG11201806405VA priority patent/SG11201806405VA/en
Priority to KR1020187020856A priority patent/KR102263211B1/ko
Publication of WO2017130864A1 publication Critical patent/WO2017130864A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to an antifouling coating composition, a coating film formed using the same, and a substrate with a coating film having the coating film on the substrate.
  • an antifouling paint composition containing an antifouling agent such as cuprous oxide (Cu 2 O) that can effectively prevent attachment of animals such as barnacles. And a method of forming an antifouling coating film on the surface of the underwater structure. More specifically, Patent Document 1 discloses that 55 to 75 parts by weight of triisopropylsilyl (meth) acrylate (a), 2 to 20 parts by weight of methoxyethyl acrylate (b), and other polymerizable components in 100 parts by weight of the monomer component. An antifouling paint composition comprising a copolymer containing 43 to 5 parts by weight of monomer (c) and an antifouling agent such as cuprous oxide has been proposed.
  • an antifouling paint composition comprising a copolymer containing 43 to 5 parts by weight of monomer (c) and an antifouling agent such as cuprous oxide has been proposed.
  • the coating film formed with such an antifouling coating composition can reduce the consumption of the coating film under a condition where it is brought into contact with water at room temperature of about 25 ° C., but the temperature is about 30 ° C. Under the condition of contacting with water, there was a problem that the amount of consumption of the coating film increased and the coating film could not be maintained for a long time.
  • the present invention has been made in view of the above circumstances, and the consumption of the coating film is not only under the condition of contact with water at a normal temperature of about 25 ° C. but also under the condition of contact with water at a high temperature of about 30 ° C. It is an object of the present invention to provide an antifouling paint composition for forming a coating film capable of suppressing the amount small and maintaining the physical properties over a long period of time. Moreover, this invention makes it a subject to provide the coating film which hardened the said antifouling coating composition, the base material with a coating film which has the said coating film on a base material, and this manufacturing method.
  • an antifouling coating composition containing a silyl polymer a monobasic acid such as rosin used as an elution aid and an antifouling agent such as cuprous oxide or It has been found that zinc oxide forms a copper salt and a zinc salt, and the ratio between the copper salt and the zinc salt has a great influence on the water resistance and wear resistance of the coating film. And further examination, when the ratio of zinc salt increases, the consumption of the coating film under high temperature conditions increases, and conversely, when the ratio of copper salt increases, the consumption under high temperature conditions, It has been found that it can be suppressed to the same level as the amount of consumption below.
  • the present inventors conducted research on the control of the ratio between the copper salt and the zinc salt.
  • the copper salt in the antifouling coating composition was obtained.
  • the present inventors have found that the amount of coating film consumed can be reduced not only under normal temperature conditions of about 25 ° C. but also under high temperature conditions of about 30 ° C., thereby completing the present invention.
  • the gist of the present invention is as follows.
  • the present invention relates to the following [1] to [8].
  • Silylacrylic copolymer (A) having a structural unit (a1) derived from triisopropylsilyl (meth) acrylate, and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond, carbon number 1.
  • An antifouling paint composition comprising 1 to 3 lower alcohol (B), an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D), the antifouling coating composition
  • An antifouling coating composition having a content of the lower alcohol (B) in the range of 0.1 to 3% by mass.
  • [2] The antifouling paint composition according to [1], wherein the mass ratio [(a1) / (a2)] of the structural unit (a1) to the structural unit (a2) is 40/60 to 95/5 object.
  • [3] The antifouling coating composition according to the above [1] or [2], wherein the content of the silylacrylic copolymer (A) in the antifouling coating composition is 5 to 40% by mass.
  • [4] The antifouling coating composition according to any one of [1] to [3], wherein the silylacrylic copolymer (A) has a weight average molecular weight (Mw) of 5,000 to 100,000. .
  • [5] A coating film obtained by curing the antifouling coating composition according to any one of [1] to [4].
  • [6] A substrate with a coating film having the coating film according to [5] on a substrate.
  • [8] A step (1) of obtaining an applied body or an impregnated body by applying or impregnating a substrate with the antifouling coating composition according to any one of [1] to [4], and the applied body or The manufacturing method of the base material with a coating film which has the process (2) which hardens the said antifouling coating composition by drying an impregnation body.
  • the amount of coating film consumed can be reduced not only under conditions of contact with water at room temperature of about 25 ° C. but also under conditions of contact with water of high temperature of about 30 ° C. It is possible to provide an antifouling paint composition for forming a coating film capable of maintaining the physical properties over a long period of time. Moreover, according to this invention, the coating film which hardened the said antifouling coating composition, the base material with a coating film which has the said coating film on a base material, and this manufacturing method can be provided.
  • the antifouling coating composition of the present invention is a silylacrylic copolymer having a structural unit (a1) derived from triisopropylsilyl (meth) acrylate and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond.
  • An antifouling paint composition comprising a coalescence (A), a lower alcohol (B) having 1 to 3 carbon atoms, an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D)
  • the content of the lower alcohol (B) in the antifouling coating composition is 0.1 to 3% by mass.
  • the antifouling coating composition of the present invention contains a silylacrylic copolymer (A) for the purpose of improving the antifouling property of the coating film, and the silylacrylic copolymer (A) is , A structural unit (a1) derived from triisopropylsilyl (meth) acrylate, and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond.
  • the “polymerizable monomer having a polymerizable double bond” constituting the structural unit (a2) means “a polymerizable double bond other than triisopropylsilyl (meth) acrylate constituting the structural unit (a1)”.
  • “(meth) acrylate” means “acrylate or methacrylate”
  • “(meth) acryl” means “acryl or methacryl”
  • “(meth) acryloyl” means “acryloyl or It means “methacryloyl”.
  • the structural unit (a1) is a structural unit derived from triisopropylsilyl (meth) acrylate.
  • the structural unit (a1) in the present invention may be a structural unit derived from any one of triisopropylsilyl acrylate (TIPSA) and triisopropylsilyl methacrylate (TIPSSMA), triisopropylsilyl acrylate, and although it may be a structural unit derived from both of triisopropylsilyl methacrylate, from the viewpoint of improving the antifouling property of the coating film, a structural unit derived from any one of triisopropylsilyl acrylate and triisopropylsilyl methacrylate It is preferable that
  • the polymerizable monomer having a polymerizable double bond constituting the structural unit (a2) is not particularly limited as long as it is a polymerizable monomer having a polymerizable double bond other than triisopropylsilyl (meth) acrylate.
  • alkyl (meth) acrylate and alkoxyalkyl (meth) acrylate are preferable, and methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BA), 2-methoxy Ethyl acrylate (MEA) and 2-methoxyethyl methacrylate (MEMA) are preferred.
  • MMA methyl methacrylate
  • EA ethyl acrylate
  • BA butyl acrylate
  • MEA 2-methoxy Ethyl acrylate
  • MEMA 2-methoxyethyl methacrylate
  • an anionic unsaturated monomer or a cationic unsaturated monomer may be further used.
  • Anionic unsaturated monomers include carboxy group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, and crotonic acid, styrene sulfonic acid, and 3- (methacryloyloxy) Examples thereof include sulfonic acid group-containing unsaturated monomers such as propanesulfonic acid and acrylamidepropanesulfonic acid. These anionic unsaturated monomers may be used partially or completely neutralized.
  • the neutralization may be performed as a monomer, or may be neutralized after the polymer is formed.
  • Examples of the base used for neutralization include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and amine compounds such as ammonia, triethanolamine and trimethylamine.
  • Examples of the cationic unsaturated monomer include one or more selected from an amino group-containing unsaturated monomer and a quaternary ammonium base-containing unsaturated monomer.
  • Amino group-containing unsaturated monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N- Diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) ) Acrylamide, 2-vinylpyridine, 4-vinylpyridine and structures obtained by neutralizing these
  • quaternary ammonium base-containing unsaturated monomer (meth) acryloyloxyethyltrimethylammonium, (meth) acryloyloxypropyltrimethylammonium, (meth) acryloylaminoethyltrimethylammonium having X ⁇ as a counter ion, ( And (meth) acryloylaminopropyltrimethylammonium, diallyldimethylammonium, 1-ethyl-4-vinylpyridinium, 1,2-dimethyl-5-vinylpyridinium, and the like.
  • X ⁇ represents an anion, preferably a halide ion, and more preferably a chloride ion.
  • the silylacrylic copolymer (A) can be produced, for example, by the following procedure. First, a solvent is put in a reaction vessel and heated to about 80 to 120 ° C. to maintain the temperature, and the triisopropylsilyl (meth) acrylate, a polymerizable monomer having a polymerizable double bond, and polymerization start A silylacrylic copolymer (A) can be obtained by dropping a mixed solution of an agent, a chain transfer agent, a solvent, and the like and performing a polymerization reaction.
  • the ratio of each content (mass) of the structural unit derived from each monomer in the silylacrylic copolymer (A) is the ratio of the charged amount (mass) of each monomer used for the polymerization reaction. Can be regarded as the same.
  • a polymerization initiator which can be used for manufacture of a silyl acryl-type copolymer (A) Various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2′-azobis (isobutyronitrile) [AIBN], 2,2 Examples include '-azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], and tert-butyl peroxyoctate [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 silylacrylic copolymer (A) is preferably 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the respective monomers.
  • the chain transfer agent that can be used for the production of the silylacrylic copolymer (A) is not particularly limited, and examples thereof include ⁇ -methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, ⁇ -terpinene; tert-dodecyl; Mercaptans such as mercaptan and n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as glycerin; and the like. These chain transfer agents may be used alone or in combination of two or more. When a chain transfer agent is used in the production of the silylacrylic copolymer (A), the amount used is preferably 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of the respective monomers.
  • Examples of the solvent that can be used in the production of the silylacrylic copolymer (A) include propylene glycol monomethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol mono Examples thereof include polyhydric alcohol monoalkyl ethers such as butyl ether; aromatic hydrocarbon solvents such as toluene, xylene and mesitylene; water and the like.
  • the amount used is not particularly limited, but is preferably 5 to 150 parts by mass with respect to 100 parts by mass in total of the respective monomers.
  • the mass ratio [(a1) / (a2)] of the structural unit (a1) to the structural unit (a2) is preferably 40/60 to 95/5, more preferably 42/58 to 85/15, and even more preferably. Is 43/57 to 75/25, more preferably 44/56 to 70/30.
  • the said mass ratio [(a1) / (a2)] can be computed from the preparation ratio of each monomer at the time of manufacturing a copolymer.
  • the weight average molecular weight (Mw) of the silylacrylic copolymer (A) is preferably 5,000 to 100,000, more preferably 10,000 to 90,000, still more preferably 15,000 to 80,000, More preferably, it is 17,000 to 70,000, and still more preferably 18,000 to 60,000.
  • the weight average molecular weight (Mw) of the silylacrylic copolymer (A) is within the above range, the spray coating workability of the antifouling coating composition is improved and the physical properties of the coating film are also improved.
  • the weight average molecular weight (Mw) of a silyl acryl-type copolymer (A) points out the value of the gel permeation chromatography (GPC) measured by the method as described in an Example.
  • the viscosity of the silylacrylic copolymer (A) is preferably 500 to 10,000 mPa ⁇ s, more preferably 1,000 to 7,000 mPa ⁇ s, and still more preferably 1,500 to 6,000 mPa ⁇ s. More preferably, it is 1,800 to 5,000 mPa ⁇ s, and still more preferably 2,000 to 4,800 mPa ⁇ s.
  • the viscosity of the silylacrylic copolymer (A) can be measured by the method described in the examples below.
  • the content of the silylacrylic copolymer (A) in the antifouling coating composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, and still more preferably 15% by mass. % Or more, more preferably 16% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more. Preferably it is 23 mass% or less.
  • the content of the silylacrylic copolymer (A) is within the above range, a coating film exhibiting excellent antifouling properties can be obtained over a long period of time, and the strength of the coating film can be further increased over a long period of time. Can be maintained.
  • the antifouling paint composition of the present invention is intended to suppress the amount of paint consumed not only under conditions of contact with water at room temperature of about 25 ° C. but also under conditions of contact with water of high temperature of about 30 ° C.
  • a lower alcohol (B) having 1 to 3 carbon atoms hereinafter sometimes simply referred to as “lower alcohol (B)”.
  • the lower alcohol (B) in this invention shall not be contained in the organic solvent (F) mentioned later.
  • the lower alcohol having 1 to 3 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. Among these, ethyl alcohol is preferable from the viewpoint of reducing the amount of consumption under conditions of contact with high-temperature water at about 30 ° C.
  • the content of the lower alcohol (B) in the antifouling coating composition is 0.1 to 3% by mass.
  • the content of the lower alcohol (B) is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, and still more preferably 0.00%.
  • an antifouling agent (C) containing a copper component and a zinc component may be used for the purpose of improving the antifouling property of the coating film.
  • the copper component in the antifouling agent (C) containing a copper component and a zinc component may be either organic or inorganic, such as cuprous oxide, rhodan copper, copper powder, copper pyrithione, and thiocyanic acid. Examples thereof include copper and cupronickel. Among these, cuprous oxide and copper pyrithione are preferable.
  • the zinc component in the antifouling agent (C) containing a copper component and a zinc component may be either organic or inorganic, such as zinc oxide, zinc pyrithione, zinc dimethyldithiocarbamate, zinc ethylenebisdithio. Carbamate, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate and the like can be mentioned, and among these, zinc oxide is preferable.
  • the copper component in the antifouling agent (C) may be used alone or in combination of two or more, and the zinc component in the antifouling agent (C) may be used alone or in combination of two or more.
  • the antifouling agent (C) it is preferable to use a combination of cuprous oxide, copper pyrithione, and zinc oxide.
  • the content of the antifouling agent (C) containing a copper component and a zinc component in the antifouling coating composition of the present invention is preferably 5 to 70% by mass from the viewpoint of improving the antifouling property of the coating film. Preferably, it is 10 to 60% by mass.
  • the antifouling agent (C) containing a copper component and a zinc component is a ratio between the copper component and the zinc component [copper from the viewpoint of reducing the consumption of the coating film even under conditions of contact with high-temperature water of about 30 ° C.
  • Component / zinc component] (mass ratio) is preferably in the range of 99/1 to 40/60, more preferably in the range of 97/3 to 50/50, and 95/5 to 60/40. More preferably, it is in the range.
  • the antifouling coating composition of the present invention may be referred to as an antifouling agent other than the antifouling agent (C) containing a copper component and a zinc component (hereinafter simply referred to as “an antifouling agent other than the antifouling agent (C)”). .) May be contained.
  • antifouling agent other than the antifouling agent (C) examples include medetomidine, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, borane-nitrogen base adducts (pyridine triphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.), ( ⁇ ) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole, N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio -4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-
  • Antifouling agents other than these antifouling agents (C) may be used alone or in combination of two or more.
  • the total content of the antifouling agent (C) in the antifouling coating composition of the present invention and the antifouling agent other than the antifouling agent (C) is preferably from the viewpoint of improving the antifouling property of the coating film. 5 to 70% by mass, more preferably 10 to 60% by mass.
  • the monocarboxylic acid compound (D) is used for the purpose of improving the surface renewability and water resistance of the coating film.
  • the monocarboxylic acid compound (D) include a compound in which one carboxy group is substituted for a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, or a saturated or unsaturated group having 3 to 40 carbon atoms.
  • a compound in which one carboxy group is substituted on a saturated alicyclic hydrocarbon group, or a compound in which one carboxy group is substituted on these substituents is preferable.
  • trimethylisobutenylcyclohexene carboxylic acid trimethylisobutenylcyclohexene carboxylic acid, versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, naphthenic acid, and these
  • the metal salt is preferred.
  • rosin and rosin derivatives mainly composed of rosin acid such as abietic acid, parastrinic acid, and isopimaric acid.
  • trimethylisobutenylcyclohexenecarboxylic 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) cyclohexa-
  • the main component (85% by mass or more) is 3-ene-1-carboxylic acid.
  • rosin and rosin derivatives examples include rosins such as gum rosin, wood rosin and tall oil rosin, and rosin derivatives such as hydrogenated rosin and disproportionated rosin.
  • the content of the monocarboxylic acid compound (D) in the antifouling coating composition of the present invention is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 2 to 10% by mass.
  • the antifouling paint composition of the present invention comprises a silylacrylic copolymer (A), a lower alcohol (B), an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D).
  • a pigment (E) an organic solvent (F), a liquidity improver (anti-sagging, settling prevention) (G), a plasticizer (H), and a dehydrating agent (I) as necessary. It may be.
  • the pigment (E) may be used for the purpose of coloring the coating film or concealing the base, or for adjusting the coating film strength to an appropriate level and for further improving the antifouling property.
  • the pigment (E) include talc, mica, clay, potash feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and zinc sulfide.
  • examples include extender pigments, petals, titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, phthalocyanine blue, and the like, and talc and petals are preferred.
  • the antifouling coating composition of the present invention contains the pigment (E)
  • the content of the pigment (E) in the antifouling coating composition is preferably 1 to 30% by mass, more preferably 4 to 25% by mass. 7 to 20% by mass is more preferable.
  • copper-based and zinc-based antifouling agents such as cuprous oxide, zinc oxide, copper pyrithione, and zinc pyrithione may have both a function as an antifouling agent and a function as a pigment, Is treated as an antifouling agent (C) containing a copper component and a zinc component.
  • an organic solvent (F) may be used for the purpose of keeping the viscosity of the antifouling coating composition small and improving spray atomization and spray coating workability.
  • aromatic hydrocarbons aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, alcohols and the like can be used, preferably aromatic carbonization. It is a hydrogen-based organic solvent.
  • aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, mesitylene and the like.
  • Examples of the aliphatic hydrocarbon organic solvent include pentane, hexane, heptane, and octane.
  • Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, ethylcyclohexane, and the like.
  • Examples of the ketone organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate.
  • Examples of the ester organic solvent include ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and the like.
  • the alcohol-based organic solvent examples include n-butanol and propylene glycol monomethyl ether.
  • the content of the organic solvent (F) in the antifouling coating composition is desired depending on the application form of the antifouling coating composition and the like. A preferable amount is determined depending on the viscosity, but usually 1 to 50% by mass is preferable. When there is too much content, malfunctions, such as a fall of sagging stop property, may generate
  • Liquidity improver (sagging prevention, settling prevention) (G)
  • the liquidity improver (G) may be used for the purpose of adjusting the viscoelasticity of the antifouling coating composition and obtaining the effect of sagging and preventing sedimentation.
  • Liquid improvers (G) include organic clay waxes (such as Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonates), organic waxes (polyethylene wax, polyethylene oxide wax, amide wax, poly Amide wax, hydrogenated castor oil wax, etc.), a mixture of organic clay wax and organic wax, synthetic fine powder silica and the like.
  • These liquidity improvers can be used singly or in combination of two or more.
  • the liquidity improver (G) Commercially available products may be used as the liquidity improver (G), and examples thereof include “DISPARON 305”, “DISPARON 4200-20”, and “DISPARON A630-20X” manufactured by Enomoto Kasei Co., Ltd.
  • the content of the liquidity improving agent (G) in the antifouling coating composition is usually preferably 0.01 to 10% by mass. 0.1 to 3% by mass is more preferable.
  • the antifouling coating composition of the present invention may use a plasticizer (H) for the purpose of improving crack resistance and water resistance of the coating film and suppressing discoloration.
  • a plasticizer (H) examples include n-paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), and polyvinyl ethyl ether. Among these, chlorinated paraffin and terpene phenol are preferable, and chlorinated paraffin is more preferable.
  • TCP tricresyl phosphate
  • These plasticizers may be used alone or in combination of two or more.
  • the plasticizer (H) a commercially available product may be used.
  • the n-paraffin is “n-paraffin” manufactured by Nippon Petrochemical Co., Ltd.
  • the chlorinated paraffin is Tosoh Corporation.
  • “Toyoparax A-40 / A-50 / A-70 / A-145 / A-150” and the like can be mentioned.
  • the content of the plasticizer (H) in the antifouling coating composition is preferably 0.1 to 10% by mass.
  • the dehydrating agent (I) may be used for the purpose of improving the storage stability of the antifouling coating composition.
  • the dehydrating agent (I) include alkoxysilane, zeolite known by the general name of “molecular sieve”, orthoester such as alumina and alkyl orthoformate, orthoboric acid, isocyanates, gypsum, and ethyl silicate. be able to. These dehydrating agents may be used alone or in combination of two or more.
  • the content of the dehydrating agent (I) in the antifouling coating composition is preferably 0.1 to 10% by mass, preferably 0.2 to 2 mass% is more preferable.
  • the content of the dehydrating agent (I) is within the above range, the storage stability of the antifouling coating composition can be kept good.
  • the antifouling paint composition of the present invention can be prepared using the same apparatus, means, etc. as those of known general antifouling paints. Specifically, a solution of a silylacrylic copolymer (A) prepared in advance, an antifouling agent (C) containing a copper component and a zinc component, a monocarboxylic acid compound (D), and other as required While stirring the solution or dispersion obtained by mixing the additives and the like, the lower alcohol (B) is added thereto, and the mixture is further stirred and mixed.
  • the coating film of the present invention is obtained by curing the antifouling coating composition of the present invention.
  • a coating film can be obtained by applying the antifouling coating composition of the present invention to a substrate or the like and then curing it.
  • the method for applying the antifouling coating composition of the present invention include known methods such as a method using a brush, a roller, and a spray.
  • the antifouling coating composition applied by the above-described method can be cured, for example, by leaving it at 25 ° C. for about 0.5 to 14 days to form a coating film.
  • the antifouling paint composition may be cured while blowing air under heating.
  • the thickness after curing of the coating film of the present invention is preferably about 30 to 1,000 ⁇ m, for example, from the viewpoint of improving the coating film strength.
  • Examples of the method for producing a coating film having this thickness include a method in which the antifouling coating composition is applied at a thickness of usually 10 to 300 ⁇ m, preferably 30 to 200 ⁇ m, and applied once to a plurality of times per application. .
  • the substrate with a coating film of the present invention has the coating film on the substrate.
  • the method for producing the coated substrate of the present invention is not particularly limited. For example, a step of obtaining an applied body or an impregnated body by applying or impregnating the antifouling coating composition to the substrate, and By a method comprising a step of curing an antifouling paint composition applied to or impregnated on a material, or a method comprising a step of affixing a coating film obtained by curing an antifouling paint composition to a substrate.
  • the substrate with a coating film of the invention can be produced.
  • the substrate is sprayed or other
  • coating or impregnating by a means is mentioned.
  • the method of curing the antifouling coating composition applied to or impregnated on the substrate is preferably a method of curing the coating composition by drying the coated body or impregnated body.
  • a method of curing by leaving or heating forcedly for about 0.5 to 14 days can be mentioned.
  • the antifouling paint composition is cured.
  • the method of sticking the film containing the obtained coating film on a base material is mentioned.
  • the antifouling paint composition of the present invention provides a long-term antifouling function for a substrate in a wide range of industrial fields such as ships, fisheries, pipelines, water systems, diving equipment, underwater propulsion bodies, power generation, harbors and civil engineering construction. Can be used to maintain the Such base materials include, for example, 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 fishing materials (ropes, fishing nets) , Fishing gear, floats, buoys, etc.), oil pipelines, water conduits, circulating water pipes, diver suits, underwater glasses, oxygen cylinders, swimsuits, torpedoes, underwater structures such as water and water outlets of thermal and nuclear power plants, seawater Examples include equipment used (seawater pumps, etc.), mega floats, gulf roads, submarine tunnels, harbor facilities, sludge diffusion prevention membranes for various civil engineering works such as canals and waterways. Among these, as a base material, a ship is preferable.
  • the antifouling coating composition of the present invention may be applied or impregnated directly on the substrate.
  • the antifouling paint composition of the present invention is also applied to a base material made of fiber reinforced plastic (FRP), steel, wood, aluminum alloy, etc., such as a water supply / drain port of a nuclear power plant, a mega float, and a ship. Can be adjusted so that the adhesion to the surface of these substrates (materials) is good.
  • the base material to which the antifouling coating composition of the present invention is applied may have a coating film already formed on the surface.
  • the antifouling coating composition of the present invention may be applied to the surface of a substrate on which a base material (undercoat) such as a rust preventive or primer has been applied in advance. Furthermore, the antifouling paint composition of the present invention is overcoated on the surface of a substrate that has already been coated with a conventional paint or is coated with the antifouling paint composition of the present invention. May be.
  • the kind of coating film which the antifouling paint composition of the present invention directly contacts is not particularly limited.
  • the measurement methods of the heating residue, weight average molecular weight (Mw), and viscosity of the obtained silylacrylic copolymers (A1) to (A4) are as follows. ⁇ Calculation method of heating residue (mass NV)> Weigh 1 g of silylacrylic copolymer (A) in a flat bottom pan, spread evenly using a wire with a known mass, dry at 125 ° C. for 1 hour, and then measure the mass of the residue and wire to obtain a heating residue ( Mass%) was calculated.
  • the weight average molecular weight (Mw) of the silylacrylic copolymer (A) is “HLC-8120GPC” manufactured by Tosoh Corporation as a measuring device, and “TSK-gel ⁇ type” manufactured by Tosoh Corporation as a separation column ( ⁇ - M) was used, and measurement was performed by gel permeation chromatography (GPC) using dimethylformamide (DMF) as an eluent.
  • the weight average molecular weight (Mw) of the silylacrylic copolymer (A) was determined as polystyrene.
  • the film thickness was measured using a non-contact type laser film thickness meter, and the difference between the film thickness before immersion and the film thickness after immersion was calculated to measure the consumption. Further, the amount of wear was measured in the same manner for the test plate after being immersed for 2 to 6 months under the above conditions. In this evaluation, it shows that the amount of consumption is restrained small, so that a numerical value is small.
  • an antifouling paint composition for forming a coating film that can reduce the consumption amount of the coating film under conditions of contact with high-temperature water and can maintain the physical properties over a long period of time. it can.
  • the antifouling coating composition of the present invention can not only reduce the consumption of the coating film under conditions of contact with water at room temperature of about 25 ° C., but also can be used under conditions of contact with water of high temperature of about 30 ° C.
  • the consumption amount of the coating film can also be suppressed small. Therefore, maintain the physical properties of coatings formed on the surface of structures such as ships, underwater structures, surfaces of structures placed in water, and pipe structures such as pipelines over a long period of time. Is possible.

Landscapes

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

Abstract

La présente invention concerne une composition de revêtement anti salissure comprenant (A) un copolymère silyl-acrylique qui comporte un motif constitutif (a1) dérivé de (méth)acrylate de triisopropylsilyle et un motif constitutif (a2) dérivé d'un monomère polymérisable ayant une double liaison polymérisable, (B) un alcool inférieur qui a 1 à 3 atomes de carbone, (C) un agent antisalissure qui contient un composant de cuivre et un composant de zinc et (D) un composé d'acide monocarboxylique, la teneur de l'alcool inférieur (B) dans la composition de revêtement antisalissure étant de 0,1 à 3 % en masse. La présente invention concerne : une composition de revêtement antisalissure pour former un film de revêtement qui est dissipé en une quantité réduite dans une condition dans laquelle le film de revêtement est en contact avec de l'eau à une température ambiante d'environ 25 °C ainsi qu'une condition dans laquelle le film de revêtement est en contact avec de l'eau à une température supérieure à environ 30 °C et qui peut maintenir les propriétés physiques de celui-ci pendant une longue durée ; un film de revêtement produit par durcissement de la composition de revêtement antisalissure ; un matériau de base fixé au film de revêtement qui comprend un matériau de base et le film de revêtement mentionné ci-dessus formé sur le matériau de base ; et un procédé de production du matériau de base fixé au film de revêtement.
PCT/JP2017/001967 2016-01-29 2017-01-20 Composition de revêtement antisalissure, film de revêtement, et matériau de base fixé à un film de revêtement Ceased WO2017130864A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780007934.XA CN108603069A (zh) 2016-01-29 2017-01-20 防污涂料组合物、涂膜和带涂膜的基材
JP2017564214A JP6737456B2 (ja) 2016-01-29 2017-01-20 防汚塗料組成物、塗膜、及び塗膜付き基材
SG11201806405VA SG11201806405VA (en) 2016-01-29 2017-01-20 Antifouling coating composition, coating film, and coating-film-attached base material
KR1020187020856A KR102263211B1 (ko) 2016-01-29 2017-01-20 방오 도료 조성물, 도막, 및 도막 부착 기재

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-015838 2016-01-29
JP2016015838 2016-01-29

Publications (1)

Publication Number Publication Date
WO2017130864A1 true WO2017130864A1 (fr) 2017-08-03

Family

ID=59398012

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/001967 Ceased WO2017130864A1 (fr) 2016-01-29 2017-01-20 Composition de revêtement antisalissure, film de revêtement, et matériau de base fixé à un film de revêtement

Country Status (5)

Country Link
JP (1) JP6737456B2 (fr)
KR (1) KR102263211B1 (fr)
CN (1) CN108603069A (fr)
SG (1) SG11201806405VA (fr)
WO (1) WO2017130864A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172683A (ja) * 1992-12-09 1994-06-21 Nippon Paint Co Ltd 防汚塗料組成物
JP2001226440A (ja) * 2000-02-17 2001-08-21 Nippon Paint Co Ltd 共重合体及び塗料組成物
JP2003277680A (ja) * 2002-03-27 2003-10-02 Kansai Paint Co Ltd 水性防汚樹脂組成物
JP2010144106A (ja) * 2008-12-19 2010-07-01 Nitto Kasei Co Ltd 防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法
JP2011530637A (ja) * 2008-08-13 2011-12-22 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ 塩の基を有するポリマーおよび該ポリマーを含む防汚コーティング組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006183059A (ja) * 1996-04-17 2006-07-13 Basf Coatings Japan Ltd 塗料組成物
JP2005082725A (ja) * 2003-09-09 2005-03-31 Nitto Kasei Co Ltd 防汚塗料組成物、該防汚塗料組成物が塗布された海中物品類、および該防汚塗料組成物を使用する防汚方法
MY146277A (en) * 2005-09-01 2012-07-31 Chugoku Marine Paints Antifouling paint composition, antifouling coating film, substrate with coating film, antifouling substrate, forming method of coating film on the surface of the substrate and antifouling method of substrate
KR20110039235A (ko) * 2008-06-11 2011-04-15 요툰 에이/에스 오염방지 코팅 조성물용 결합제 및 결합제를 포함하는 오염방지 코팅 조성물
JP5142150B2 (ja) * 2008-10-02 2013-02-13 Ｎｋｍコーティングス株式会社 共重合体組成物、防汚塗料組成物、施工方法及び構造物
KR101647903B1 (ko) * 2011-11-14 2016-08-11 주고꾸 도료 가부시키가이샤 방오도료 조성물, 방오도막, 방오기재 및 방오기재의 제조방법
WO2014010702A1 (fr) * 2012-07-12 2014-01-16 日立化成ポリマー株式会社 Résine polyester pour des matières de revêtement antisalissure, son procédé de fabrication, composition de matière de revêtement antisalissure, film de revêtement antisalissure et base antisalissure
ES2665573T3 (es) * 2013-03-15 2018-04-26 Nitto Kasei Co., Ltd. Composición de recubrimiento antiincrustante, película de recubrimiento antiincrustante formada usando dicha composición y artículo recubierto que tiene película de recubrimiento antiincrustante sobre la superficie
BR112015026577A2 (pt) * 2013-04-23 2017-07-25 Chugoku Marine Paints composição de revestimento anti-incrustante, película de revestimento anti-incrustante, substrato anti-incrustante e método para produzir substrato anti-incrustante
MY182675A (en) * 2013-04-24 2021-01-29 Nitto Kasei Co Ltd Antifouling paint composition, copolymer for antifouling paint composition and method for manufacturing same, and painted object having on surface antifouling paint film formed using said composition
CN106164189B (zh) * 2014-04-10 2018-09-25 关西涂料株式会社 防污涂料组合物以及涂装其而成的涂装物品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172683A (ja) * 1992-12-09 1994-06-21 Nippon Paint Co Ltd 防汚塗料組成物
JP2001226440A (ja) * 2000-02-17 2001-08-21 Nippon Paint Co Ltd 共重合体及び塗料組成物
JP2003277680A (ja) * 2002-03-27 2003-10-02 Kansai Paint Co Ltd 水性防汚樹脂組成物
JP2011530637A (ja) * 2008-08-13 2011-12-22 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ 塩の基を有するポリマーおよび該ポリマーを含む防汚コーティング組成物
JP2010144106A (ja) * 2008-12-19 2010-07-01 Nitto Kasei Co Ltd 防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法

Also Published As

Publication number Publication date
JPWO2017130864A1 (ja) 2018-10-11
KR102263211B1 (ko) 2021-06-09
KR20180091926A (ko) 2018-08-16
JP6737456B2 (ja) 2020-08-12
SG11201806405VA (en) 2018-08-30
CN108603069A (zh) 2018-09-28

Similar Documents

Publication Publication Date Title
JP4837668B2 (ja) 防汚塗料組成物、防汚塗膜、塗膜付き基材、防汚性基材、基材表面への塗膜の形成方法および基材の防汚方法
KR102656962B1 (ko) 방오도료 조성물, 방오도막, 방오도막 부착 기재 및 그의 제조방법, 및 보수방법
CN109415596B (zh) 防污涂料组合物、防污涂膜、带防污涂膜的基材及其制造方法、以及防污方法
JP6638958B2 (ja) 防汚塗料組成物、防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに防汚方法
JP6067199B1 (ja) 防汚塗料組成物、防汚塗膜、防汚基材、防汚基材の製造方法および防汚塗料組成物の貯蔵方法
JP2016089167A (ja) 防汚塗料組成物、防汚塗膜および防汚基材、ならびに防汚基材の製造方法
JP6909894B2 (ja) 防汚塗料組成物、防汚塗膜、防汚基材及びその製造方法
JP7628039B2 (ja) 防汚塗料組成物
WO2017094768A1 (fr) Composition de revêtement antisalissure, film de revêtement antisalissure, base antisalissure, et procédé de fabrication de base antisalissure
KR102171055B1 (ko) 방오 도료 조성물, 방오 도막, 방오 도막 부착 기재 및 그의 제조 방법, 및 방오 방법
JPWO2019216413A1 (ja) 防汚塗料組成物、防汚塗膜、防汚塗膜付き基材及び防汚方法
JP7686419B2 (ja) 防汚塗料組成物
WO2020235382A1 (fr) Composition de revêtement antisalissure
JP7561567B2 (ja) 防汚塗料組成物
JP6737456B2 (ja) 防汚塗料組成物、塗膜、及び塗膜付き基材
JP6596802B2 (ja) 摩擦抵抗低減塗膜形成用の塗料組成物、塗膜、及び塗膜付き基材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17744094

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017564214

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187020856

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020187020856

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 11201806405V

Country of ref document: SG

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17744094

Country of ref document: EP

Kind code of ref document: A1