WO2019146163A1 - 防錆処理された金属部材およびコート塗料 - Google Patents

防錆処理された金属部材およびコート塗料 Download PDF

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Publication number
WO2019146163A1
WO2019146163A1 PCT/JP2018/036885 JP2018036885W WO2019146163A1 WO 2019146163 A1 WO2019146163 A1 WO 2019146163A1 JP 2018036885 W JP2018036885 W JP 2018036885W WO 2019146163 A1 WO2019146163 A1 WO 2019146163A1
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Prior art keywords
coated
mass
coating
film
leafing
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Ceased
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PCT/JP2018/036885
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English (en)
French (fr)
Japanese (ja)
Inventor
和利 榊原
靖高 長谷川
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Togo Seisakusho Corp
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Togo Seisakusho Corp
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Priority to CN201880087834.7A priority Critical patent/CN111655901B/zh
Priority to EP18901892.2A priority patent/EP3748036B1/en
Priority to US16/958,827 priority patent/US12227852B2/en
Publication of WO2019146163A1 publication Critical patent/WO2019146163A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • 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
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2303/00—Functional details of metal or compound in the powder or product
    • B22F2303/40—Layer in a composite stack of layers, workpiece or article
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium

Definitions

  • the present invention relates to a rustproofed metal member having a zinc composite coating and a coated coating formed on the surface, and a coating paint for rustproofing treatment.
  • a technology for rustproofing a metal member by forming a zinc composite coating on the surface of the metal member is conventionally known. Due to the anticorrosion action (a sacrificial anticorrosion action) of zinc contained in the zinc composite coating, this kind of rustproofed metal member is unlikely to be rusted. Moreover, the technique which maintains the anticorrosion effect
  • a zinc composite film is formed by applying metal powder-chromium oxide treatment (so-called dacrotize (registered trademark) treatment) to the surface of a plated metal member, and further, a water system is applied on the zinc composite film.
  • metal powder-chromium oxide treatment so-called dacrotize (registered trademark) treatment
  • a water system is applied on the zinc composite film.
  • a technique for forming a coated film mainly composed of an aqueous treatment liquid containing a resin and a silica material According to the technology disclosed in Patent Document 1, the zinc composite film and the metal member can be isolated from the outside by the coated film, so that the anticorrosive action of the zinc composite film can be maintained for a relatively long time. Further, since the coat film contains a resin material, it may be able to deform following the elastic deformation of the metal member. Therefore, even when using, for example, a hose clamp or a spring as a metal member, there is a possibility that the metal member and the zinc composite coating can be
  • Patent Document 1 it is difficult to control the viscosity of the coating material, and it is difficult to make the coating film thin.
  • the coated film is white, black, transparent, etc., depending on the color of the extender pigment. For this reason, when a part of the coated film is missing due to chipping, cracking, peeling, etc. and the zinc composite film is exposed, the zinc composite film of the exposed part is displayed against the extender pigment color of the coated film around the exposed part. Silver may be noticeable on the surface.
  • Patent Document 2 discloses a zinc fine particle-dispersed resin on the surface of a rare earth metal-based permanent magnet in order to provide a corrosion-resistant rare earth metal-based permanent magnet in which the occurrence of white rust is suppressed while utilizing the sacrificial anticorrosion effect of zinc potential.
  • a technique for forming a film and further forming an aluminum fine particle dispersed resin film on the surface thereof According to the technique disclosed in Patent Document 2, the aluminum fine particle dispersed resin film as the upper layer exhibits excellent corrosion resistance, and the zinc fine particle dispersed resin film as the lower layer suppresses the corrosion of the magnet main body by sacrificial corrosion prevention.
  • Patent Document 2 the object of the rustproofing treatment is limited to only the rare earth permanent magnet, and the application to other metal members including an elastic material is neither described nor suggested, and naturally occurs frequently depending on the product application. Cases where part of the coated film is missing due to chipping, cracking, peeling, etc. to be obtained are not considered.
  • Patent Document 2 from the viewpoint of improving the appearance, only white rust caused by sacrificial corrosion of zinc in the zinc fine particle dispersed resin film is regarded as a problem. In a wide range of applications such as machine parts, preventing rusting of metal members that can affect the mechanical strength of the entire product is more important than preventing white rust, but Patent Document 2 does not describe red rusting. For this reason, in the prior art, it was difficult to provide the rustproof performance excellent to the rustproofed metal member.
  • the present invention has been made in view of the above circumstances, and by improving the performance of a protective coating film formed thin on a zinc composite coating having a sacrificial corrosion protection effect, an appearance due to partial loss of the coating film
  • An object of the present invention is to provide an antirust-treated metal member which is capable of reducing defects and exerting a sacrificial anticorrosion effect of zinc more than before, and which is particularly excellent in antirust performance to red rust.
  • the anticorrosion-treated metal member of the present invention for solving the above problems is A metal member of a predetermined shape, A zinc composite coating formed on the surface of the metal member; And a coated film obtained by coating and drying a coated paint on the zinc composite film,
  • the coated paint comprises a coated substrate comprising an organic solvent and a resin material dissolved in the organic solvent, and an extender pigment and an anticorrosive pigment dispersed and held in the coated substrate,
  • the anticorrosion pigment is characterized in that it contains aluminum flakes which are not subjected to leafing processing.
  • the coated paint of this invention which solves the said subject, A coating composition for anticorrosion treatment which is applied onto a zinc composite coating and dried to form a coated coating, A coated substrate comprising an organic solvent and a resin material dissolved in the organic solvent, and an extender pigment and an anticorrosion pigment dispersed and held in the coated substrate,
  • the anticorrosion pigment is characterized in that it contains aluminum flakes which are not subjected to leafing processing.
  • the present invention by improving the performance of a thin coating formed on a zinc composite coating having a sacrificial anticorrosion effect, it is possible to reduce appearance defects due to partial loss of the coating and also to reduce the appearance of zinc. It becomes possible to exhibit a sacrificial anticorrosion effect more than before, and to provide an antirust-treated metal member which is excellent in anticorrosion performance particularly to red rust.
  • the numerical range “x to y” described in the present specification includes the lower limit x and the upper limit y within the range. Then, the upper limit value and the lower limit value, and the numerical values listed in the examples can be combined arbitrarily to constitute a numerical range. Furthermore, numerical values arbitrarily selected from these numerical ranges can be used as new upper and lower numerical values.
  • the anticorrosion-treated metal member of the present invention (hereinafter, appropriately abbreviated as anticorrosion metal member) comprises a metal member of a predetermined shape, a zinc composite film formed on the metal member, and zinc as a coating material. And a coated film which is applied and dried on the composite film.
  • the coated film in the rustproof metal member of the present invention is particularly excellent when the present invention is applied to a metal member (for example, a hose clamp, a spring, etc.) in which chipping, cracking or peeling of the film easily occurs by elastic deformation during use. Demonstrate anti-corrosion performance.
  • a metal member for example, a bolt or the like
  • a metal member which does not elastically deform at the time of use may be used according to the request for rust prevention.
  • the metal member has a predetermined shape.
  • the predetermined shape of the metal member referred to here is a concept encompassing the shapes of various parts that require rust prevention in various industrial fields such as clip, spring, plate, bolt, hose clamp, etc. It does not refer to
  • a general coating containing zinc can be used as the zinc composite coating according to the present invention.
  • existing films such as Dacrotize (registered trademark), Geomet (registered trademark), Zintek (registered trademark), Raffle (registered trademark), etc.
  • zinc composite coatings treated by a treatment method examples include zinc composite coatings treated by a treatment method. These zinc composite coatings can be preferably used because they are excellent in antirust performance.
  • the coat film according to the present invention is formed by applying and drying a coating paint comprising a specific component.
  • the coated paint forming the coated film includes a coated substrate, and an extender pigment and an anticorrosion pigment dispersed and held in the coated substrate.
  • the coated substrate comprises an organic solvent and a resin material dissolved in the organic solvent.
  • the coating composition according to the present invention is a component (that is, a lacquer-based material) containing an anticorrosive pigment, an extender pigment, a resin material and an organic solvent as components.
  • the organic solvent functions as a medium (ie, solvent) for dissolving the resin material.
  • leafing processing is surface processing widely used for metal pigments such as aluminum (aluminum), and metal pigment particles dispersed in a paint by covering the surface of metal pigment particles with a stearate etc. The purpose is to float the surface by surface tension to align and orient on the coating film surface.
  • Leafing is mainly applied to well-coated flake (thin leaf, flake, scaly) particles in order to improve the coating property.
  • the flake-like metallic pigment which has been subjected to leafing processing can be further improved as to coverage and can efficiently improve the appearance such as reflectance with the minimum compounding amount, and therefore it is generally used as a pigment of metallic color (metallic color) paint It is used.
  • the aluminum flakes used in the present invention are flakes, thin leaves, scaly flakes, but are not subjected to leafing processing.
  • Aluminum flakes not subjected to leafing treatment are generally commercially available as non-leafing aluminum flakes and non-leafed aluminum flakes.
  • aluminum flakes not subjected to leafing processing are appropriately referred to as non-leafing aluminum flakes.
  • Non-leafing aluminum flakes are incorporated as part of the anti-corrosive pigment in the present invention.
  • Non-leafing aluminum flakes are arranged in random directions without being affected by surface tension in the paint to the coating surface. For this reason, it is possible for the non-leafing aluminum flakes to be in a state of penetrating the coated film after drying.
  • the non-leafing aluminum flakes used in the present invention also serve as color pigments. That is, by the combination of non-leafing aluminum flakes, the coated film in the present invention has a metallic color, and has the same color as the underlying zinc composite film. For this reason, even when only the coating film is partially lost and the underlying zinc composite film is exposed, the exposed zinc composite film and the surrounding coating film have an appearance consistency, and the coating film is missing. It is hard to stand out.
  • the non-leafing aluminum flakes are not arranged in parallel on the surface of the film, and in a preferred embodiment, most of the non-leafing aluminum flakes are present penetrating the coated film. Since there is an interface between the particle surface of the non-leafing aluminum flake penetrating the coated film and the resin substrate, it becomes easier to pass trace moisture etc. compared to the leafing aluminum flake arranged in parallel on the film surface, The penetrating non-leafing aluminum flakes themselves can contribute to sacrificial corrosion protection. For this reason, the non-leafing aluminum flakes in the present invention are a part of the rust preventive pigment.
  • the interface between the zinc composite coating and the coated coating can also pass moisture and current due to the presence of the penetrated non-leafing aluminum flakes. For this reason, even if metallic zinc remains coated on the surface with the coated film (that is, even if there is no partial chipping or the like in the upper coated film) and the metallic zinc in the lower zinc composite coating is not directly exposed to the outside ), It is possible to contribute to sacrificial corrosion protection through the interface between the zinc composite coating and the coated coating and the interface between the particle surface of the non-leafing aluminum flakes and the resin substrate.
  • the coated film by the coated paint of the present invention has a relatively wide range of sacrificial corrosion protection by zinc even in the presence of small chipping / cracking / peeling as compared with the coating by the conventional coated paint, and the final The anticorrosion performance in the original meaning of suppressing the progress of the rust to a metal member main body and the physical property fall of the metal member by it is high.
  • the appearance of the rustproof metal member of the present invention is the same silver color as the zinc composite film.
  • the rustproof metal member of the present invention is excellent in the scratched appearance as well as the scratched corrosion resistance.
  • Non-leafing aluminum flakes that can be used in the present invention may be commercially available ones, for example, non-leafing aluminum paste available from Toyo Aluminum Co., Ltd.
  • non-leafing aluminum flakes penetrate the coating film, those having an average particle diameter equal to or greater than the coating thickness formed per one coating of the coating film are desirable.
  • the coated film on the zinc composite film in the present invention is formed by one to two applications, in consideration of the uniformity of the film and the coating cost. In the case of double coating, it is sufficient to adjust the size so that the non-leafing aluminum flakes to be blended have an average particle diameter exceeding the dry film thickness of the corresponding coating for each coating. That is, the value of the average particle diameter D50 of the non-leafing aluminum flakes is preferably 1/2 or more of the average thickness of the coated film.
  • the average particle diameter D50 of the non-leafing aluminum flakes is measured by mass cumulative particle diameter by a laser diffraction scattering particle size distribution measurement method.
  • the hypotheses of the mechanism that exerts the same rust prevention effect as that of the one-time application even with the two-time application are described with reference to the drawings after the examples.
  • non-leafing aluminum having an average particle diameter D50 of 6 ⁇ m according to the present invention is also applied twice so that the coating dry thickness per coat is 5 ⁇ m each and the total dry thickness is 10 ⁇ m.
  • the non-leafing aluminum flakes exhibited an anticorrosion function to an extent that they were considered to have penetrated the coated film. This supports the above hypothesis. From the currently available non-leafing aluminum flakes, it is desirable to appropriately select the average particle size of the non-leafing aluminum flakes to be used, taking into account the required dry film thickness, appearance and other factors.
  • the average particle diameter D50 of the non-leafing aluminum flakes preferably selected for coated film formation requiring thickness reduction is 6 to It is 22 ⁇ m, more preferably 6 to 15 ⁇ m.
  • the blending ratio of non-leafing aluminum flakes preferably selected for forming a coated film is preferably 1.0 to 4.5 parts by mass, more preferably 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the coated paint.
  • the parts by mass particularly preferably 1.0 to 3.0 parts by mass.
  • the desirable blending ratio of the non-leafing aluminum flakes to the coated film after drying is 2.0 to 10.0 mass%, more preferably 2.0 to 9 mass% with respect to 100 mass% of the coated film (corresponding to the solid content of the coating).
  • the content is preferably 0. 0% by mass, particularly preferably 2.0 to 7.0% by mass.
  • the blending ratio of non-leafing aluminum flakes in the coated paint or the coated film is too small, it becomes difficult to effectively exhibit the effect of the non-leafing aluminum flakes.
  • the blending ratio of the non-leafing aluminum flakes in the coated paint or the coated film is too large, the insulating property or adhesion of the coated film is reduced.
  • the resin material according to the present invention it is preferable to use a resin material which is excellent in adhesion to metal and water resistance and has a low viscosity in a dissolved state.
  • resin materials include epoxy resins, phenol resins and acrylic resins.
  • the epoxy resin include various epoxy resins of bisphenol A type, bisphenol F type, phenoxy type, novolac type, aliphatic type and glycidyl amine type.
  • mold and a bisphenol F type is mentioned, A bisphenol A epoxy resin is especially preferable.
  • particularly preferable phenol resins include resol-type phenol resins.
  • a combination of epoxy resin such as bisphenol A type epoxy resin and resol type phenol resin in a mass ratio of 16: 1 as a combination having the curing action by cross reaction and being excellent in thixotropy, insulation property, coating film elasticity and appearance.
  • a mixture of 2: 1, more preferably 12: 1 to 2: 1, particularly preferably 9: 1 to 2: 1, and still more preferably 4: 1 to 2: 1 can be mentioned.
  • the resin material is preferably contained in an amount of 10 to 20 parts by mass, more preferably 13 to 18 parts by mass, and particularly preferably 14 to 16 parts by mass with respect to 100 parts by mass of the coating material containing a solvent.
  • the content of the resin material is preferably 24 to 40% by mass, more preferably 30 to 38% by mass, and particularly preferably 31 to 35% by mass, based on 100% by mass of the coating film (corresponding to the solid content of the coating). If the blending ratio of the resin material to the coated paint or the coated film (corresponding to the solid content of the paint) is too small, the coated film becomes hard. On the other hand, when the compounding ratio of the resin material to the coated paint or the coated film (corresponding to the solid content of the paint) is too large, it becomes difficult to secure an appropriate blended amount of the other components.
  • the coating paint preferably further contains an imidazole-based curing accelerator.
  • an imidazole-based curing accelerator as a curing accelerator for epoxy resin, the color of the coated film in the present invention can be made closer to the color of the zinc composite film, and appearance defects due to partial loss of the coated film can be made more effective. It becomes possible to suppress. It is considered that this is because the imidazole-based curing accelerator does not have a coloring functional group such as an amine contained in organic acid hydrazine.
  • imidazole-based curing accelerator examples include imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl-imidazole, 1- Examples include cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like.
  • the imidazole curing accelerator may be used alone or in combination of two or more.
  • the compounding ratio of the curing accelerator of the epoxy resin is preferably 0.1 to 0.5 parts by mass, and more preferably 0.2 to 0.4 parts by mass with respect to 100 parts by mass of the coating material. Further, the blending ratio of the curing accelerator of the epoxy resin is preferably 0.2 to 1.1% by mass with respect to 100% by mass of the coating film (corresponding to the solid content of the coating), and 0.4 to 0.9 It is more preferable to use mass%.
  • extender pigments can be suitably used.
  • suitable soft extender pigments are talc, magnesium silicate, aluminum sulfate, barium sulfate and the like.
  • the preferable blending ratio of the body pigment to 100 parts by mass of the coated paint of the present invention is 10 to 30 parts by mass, more preferably 19 to 27 parts by mass, and particularly preferably 21 to 25 parts by mass.
  • the preferred blending ratio of the body pigment to 100% by mass of the coated film (corresponding to the solid content of the coating) is 30 to 57% by mass, more preferably 45 to 54% by mass, and particularly preferably 48 to 52% by mass is there. If the blending ratio of the extender pigment to the coated paint or the coated film (corresponding to the solid content of the paint) is too small, the coated film may be hardened or the corrosion resistance may be adversely affected.
  • the blending ratio of the body pigment to the coating material or the coating film (corresponding to the solid content of the coating material) is too large, it becomes difficult to uniformly disperse in the coating material, or the adhesion of the coating film decreases. Sometimes.
  • color pigments having strong coloring ability and hiding power such as carbon black, titanium oxide (titanium white) and triiron ferric oxide do not apply to the extender pigment or the rust preventive pigment in the present invention, the color request Accordingly, it can be appropriately blended, in which case a part of the blending ratio of the extender pigment is replaced with the color pigment.
  • the coated paint of the present invention may contain an anticorrosive pigment other than non-leafing aluminum flakes. It is preferable to use at least one of phosphate and silicate as an anticorrosion pigment for coating paints. Thereby, it is possible to suppress the elution of zinc in the zinc composite coating, and therefore, the anticorrosion action of the zinc composite coating can be maintained for a long time.
  • Preferred anti-corrosive pigments include zinc phosphate, magnesium phosphate, aluminum phosphate, calcium phosphate, zinc tripolyphosphate, magnesium tripolyphosphate, aluminum tripolyphosphate and calcium tripolyphosphate.
  • the compounding ratio of the anticorrosive pigment to 100 parts by mass of the coated paint is preferably 2.5 to 8.5 parts by mass, more preferably 3 to 8 parts by mass, ⁇ 7 parts by weight are particularly preferred.
  • the compounding ratio of the anticorrosive pigment to the coated film is 100 mass% is 5 to 18 mass%, more preferably 6 to 17 mass %, Particularly preferably 8 to 15% by mass.
  • the blending ratio of the anticorrosive pigment other than the non-leafing aluminum flakes to the coated paint or the coated film is too small, the corrosion resistance of the coated film is adversely affected.
  • the blending ratio of the anticorrosive pigment other than the non-leafing aluminum flakes to the coated paint or coated film is too large, the adhesion of the coated film may be reduced.
  • One example of a preferable blending ratio of each component in the coat according to the present invention is 30 to 38% by mass of a resin material and 2 to 9% by mass of non-leafing aluminum flakes with respect to 100% by mass of a coat (corresponding to coating solid content). And 6 to 17% by mass of an anticorrosive pigment other than non-leafing aluminum flakes, 45 to 54% by mass of an extender pigment, and 0.2 to 1.1% by mass of an imidazole-based curing accelerator.
  • one example of a more preferable blending ratio of each component in the coated film according to the present invention is 31 to 35% by mass of a resin material with respect to 100% by mass of a coated film (corresponding to coating solid content) 7% by mass, 8 to 15% by mass of a rust preventive pigment other than non-leafing aluminum flakes, 48 to 52% by mass of an extender pigment, and 0.4 to 0.9% by mass of an imidazole-based curing accelerator.
  • organic solvent is blended in the coated paint of the present invention.
  • the organic solvent it is preferable to use one having high boiling point and high solubility of the resin material such as aromatic solvents, alcohol solvents, ketone solvents and the like.
  • aromatic solvents include toluene, xylene, ethylbenzene, phenol, etc.
  • Preferred ketone solvents include methyl ethyl ketone, methyl butyl ketone, etc.
  • Preferred alcohol solvents are ethylene glycol monobutyl ether, butanol, ethanol, methanol And the like, and these may be used alone or as a mixed solvent of two or more.
  • an aromatic solvent comprising at least one selected from toluene, xylene, ethylbenzene and phenol
  • an alcohol solvent comprising at least one selected from ethylene glycol monobutyl ether, butanol, ethanol and methanol, methyl ethyl ketone
  • it is at least 1 type chosen from the ketone solvent which consists of at least 1 type chosen from methyl butyl ketone.
  • the compounding ratio of the organic solvent in the coating paint can be appropriately adjusted so that the coating paint can be appropriately applied on the zinc composite film. That is, the coated paint of the present invention contains an amount of organic solvent suitable for application.
  • the blending ratio of the organic solvent to 100 parts by mass of the coating material can be, for example, 48 to 61 parts by mass, or 50 to 59 parts by mass.
  • One example of the preferable blending ratio of each component in the coating paint according to the present invention is 13 to 18 parts by mass of resin material, 1.0 to 4.0 parts by mass of non-leafing aluminum flake, non-leafing with respect to 100 parts by mass of the coating composition 3 to 8 parts by mass of a rust preventing pigment other than aluminum flakes, 19 to 27 parts by mass of an extender pigment, 0.1 to 0.5 parts by mass of an imidazole-based curing accelerator, and 48 to 61 parts by mass of an organic solvent.
  • 14-16 mass parts of resin materials and 1.0-3.0 mass parts of non-leafing aluminum flakes are 100 mass parts of coating paints. 4 to 7 parts by mass of an anticorrosive pigment other than non-leafing aluminum flakes, 21 to 25 parts by mass of an extender pigment, 0.2 to 0.4 parts by mass of an imidazole-based curing accelerator, and 50 to 59 parts by mass of an organic solvent.
  • the pencil hardness of the coated film in the rustproof metal member of the present invention is preferably F to B. More preferably, the pencil hardness is F. When the pencil hardness of the coat film is within this range, the coat film is softened and the strength of the coat film is sufficiently ensured.
  • the term "pencil hardness” as used herein refers to scratch hardness according to JIS K 5600-5-4 (old JIS K 5400-8-4-2).
  • the coating film of the present invention preferably has a color difference ⁇ B with the underlying zinc composite film of 10 degrees or less, more preferably 5 degrees or less, and particularly preferably 3 degrees or less.
  • the measured value of hose ASSY corrosion resistance in the coating film of this invention it is desirable that it is 1500 hours or more also in any of normal temperature and heat resistance.
  • the volume resistance of the coated film of the present invention is preferably 1 ⁇ 10 13 ⁇ ⁇ cm or more.
  • the Erichsen peel diameter of the coated film of the present invention is preferably 3 mm or less.
  • the TI value of the coated film of the present invention is desirably 3.5 or more.
  • the rustproof metal member of the present invention contains non-leafing aluminum flakes in the coat film, it is possible to further enhance the sacrificial anticorrosion effect of the zinc composite film and to suppress appearance defects due to partial loss of the coat film. Can.
  • the coating composition of the present invention is a lacquer system, it can be applied uniformly as a thin film, and by devising the resin composition, the coating properties of the coating composition, the insulation property of the coating film, adhesiveness, curability, etc. are effectively achieved. It can be improved.
  • the coating film becomes less likely to be colored, and the color of the coating film approaches the silver color of the zinc composite film of the base, so the coating film is damaged. Poor appearance can be suppressed more effectively.
  • the present invention exhibits excellent corrosion resistance of parts such as iron clips and iron hose clamps used in high heat and high corrosion environments (snow metal salt, presence of sea salt particles, electrolytic corrosion with noble substances).
  • the rustproof metal member and the coated paint of the present invention will be specifically described.
  • the present invention is not limited by the following examples.
  • the detail of the physical-property test of a coating paint can refer to each item of JIS K 5492 (2014) aluminum paint, and the JIS K 5600 paint general test method.
  • FIG. 1 The perspective view which represents typically what used the hose clamp as an anticorrosion metal member of a predetermined shape by this-application Example is FIG.
  • FIG. 2 is sectional drawing which expands the surface structure of the anticorrosion metal member manufactured by the Example, and represents it typically.
  • the anticorrosion metal member 1 of FIG. 2 includes a metal member 2, a zinc composite film 3 formed on the surface of the metal member 2, and a coat film 4 formed on the zinc composite film 3 .
  • the metal member 2 is made of steel and is generally in the form of the hose clamp shown in FIG.
  • the metal member having the zinc composite coating used in the examples was manufactured as follows. First, a steel hose clamp (plate thickness 0.7 mm, plate width 8 mm, diameter (free diameter) 8.6 mm) prepared in advance is shot peened on a metal member to roughen the oxide film on the surface of the metal member did. 20 to 25 ° C Geomet 720 (a registered trademark of NOF Metal Coatings Co., Ltd. A combination of zinc and aluminum flakes with a special inorganic binder, commercially available with a silver appearance) Soak in the treatment solution for 2 to 6 minutes. After immersion, the Geomet 720 treatment liquid was uniformly deposited on the metal member using a dip spin apparatus, and heated in an electrically heated hot air circulating furnace at 320 to 360 ° C.
  • Geomet 720 a registered trademark of NOF Metal Coatings Co., Ltd.
  • a metal member (hereinafter referred to as “zinc coated metal member”) having a zinc composite coating formed on the surface with a coating weight of 220 mg / dm 2 was obtained.
  • the coating material used as the raw material of a coating film was manufactured as follows. First, 12.4 parts by mass of bisphenol type epoxy resin and 3.1 parts by mass of resol type phenol resin (blended as a resin material. The mass ratio of epoxy resin: phenol resin is 4: 1), 0.3 mass Part of imidazole (formulated as a curing accelerator for epoxy resin), 23.2 parts by mass of magnesium silicate (average particle diameter 7 ⁇ m, formulated as an extender pigment), and 5.6 parts by mass of aluminum tripolyphosphate (average particle size) Prepare 1 ⁇ m, formulated as an anticorrosive pigment), 1.7 parts by mass of non-leafing aluminum flakes (average particle diameter 15 ⁇ m, formulated as an anticorrosive pigment), and 53.7 parts by mass of methyl ethyl ketone (formulated as an organic solvent) did.
  • a mixture of a resin material, an anticorrosive pigment, an extender pigment and a coloring pigment (hereinafter referred to as a coated powder material) was stirred for 180 minutes by a ball mill.
  • the coated powder material after stirring was mixed with an organic solvent to prepare a coated paint.
  • the resin material was completely dissolved in the organic solvent.
  • Various pigments, including non-leafing aluminum flakes, were dispersed in the organic solvent.
  • the coated paint of Production Example 1 obtained as a result of mixing exhibited a silver color.
  • the above-described zinc-coated metal member was immersed in the coated paint (normal temperature) produced in Production Example 1 for 2 to 6 minutes. After immersion, the coated paint was uniformly attached to the zinc-coated metal member using a dip spin apparatus, and heated at 180 ° C. for 20 minutes in an electrically heated hot air circulating furnace. After heating, it was allowed to cool at room temperature. By repeating the above-described process twice, a coated film produced from the coated paint of Production Example 1 was formed on the zinc-coated metal member. The applied amount of the coated film according to JIS K 5600-1-7 (mass method) at this time was 150 mg / dm 2 . The coating thickness converted from the density to the average film thickness is 10 ⁇ m (twice coating of 5 ⁇ m thickness).
  • the coating materials according to Examples 2 to 20 and Comparative Examples 1 and 2 and the rust-proof metal members coated with the same according to Examples 2 to 20 and Comparative Examples 1 to 2 were obtained by changing the types and blending ratios of the raw materials and the baking conditions in the same procedure. Changes in the types of raw materials, particle sizes, compounding ratios, baking temperatures and other conditions are shown in detail in the film component column of Tables 1 to 5. The units in the film component column are all% by mass excluding the column of "epoxy resin: phenol resin ratio".
  • the Erichsen peeling diameter was measured for each of the rustproof metal members.
  • the Erichsen peel diameter causes a collision with the same momentum and indicates the size of the chipping off of the coated paint. The smaller the peeling diameter, the better the performance.
  • the pencil scratching hardness of the coated film was measured for each of the rustproof metal members.
  • the pencil hardness was measured in accordance with JIS K 5600-5-4.
  • the rustproof performance evaluation test (a salt spray test according to JIS Z 2371) was performed on each rustproof metal member.
  • the rustproof performance evaluation test was conducted using five rustproof metal members of each example or comparative example under three test conditions.
  • the results (in units of hours) of the antirust performance evaluation test are shown in the column of SST hose ASSY (corrosion resistance) in Tables 1 to 5. After the application and drying of the coating material, the results of the non-scratched member were described in the "normal temperature (scratch free)" column.
  • thermogravimetric reduction is an index of the thermal decomposition temperature of the resin component, it is an index of heat resistance.
  • the color difference ⁇ B between the color tone b * (SCE, regular reflection light removal) of the coating film at normal temperature and the color tone b * (SCE, regular reflection light removal) of the zinc composite film at normal temperature was measured for each rustproof metal member. Further, the color difference ⁇ B between the color tone b * (SCE) of the coated film fired at 200 ° C. and the color tone b * (SCE) of the coated film fired at 180 ° C. was also measured.
  • the color difference ⁇ B is a value measured based on JIS Z 8730 using a spectrocolorimeter (model CM-3600 d, Konica Minolta) as a color difference meter.
  • Comparative Example 1 in which leafing aluminum flakes were blended instead of non-leafing aluminum flakes, the aluminum flakes were flocculated and floated before the storage stability test was conducted, and they were not dispersed, and thus the ordinary coating film test was not conducted.
  • Comparative Example 2 in which titanium oxide was blended instead of non-leafing aluminum flakes was inferior in adhesion and corrosion resistance, and of course color difference.
  • the corrosion resistance is poor as in Example 12, and the appearance is also reduced to such an extent that chipping can be visually discriminated by the color difference with the lower layer. If the blending amount of the non-leafing aluminum flakes is too large from the common sense amount, the appearance is not a problem as in Example 13, but the resistance value is too low and the corrosion resistance is reduced, and the adhesion is also reduced.
  • Example 14 the baking temperature was changed. It shows that browning of the resin affects the appearance if the baking temperature selected according to the resin used is not used.
  • Example 15 and 16 the compounding ratio of the epoxy resin and the resol type phenol resin was changed. In Example 15, the TI value is too low, the paintability is poor, the resistance value is low, and the corrosion resistance is affected. In Example 16, since there were too few resol type phenol resin, since the curability was bad and it was not able to fully harden, other physical properties were not able to be measured.
  • Example 17 the corrosion resistance was adversely affected by the fact that the blending amount of the extender pigment is too small, and conversely, it was shown that the adhesion was adversely affected by the fact that the blending amount of the extender pigment was too large. Similarly, it was shown that the corrosion resistance is adversely affected if the rust preventive pigment is too small in Example 19 and the adhesion is adversely affected if it is too large in Example 20. Furthermore, if the curing accelerator was too large in Example 21, the coating film was thickened, so that a normal coating film test was not performed. Moreover, in Example 22 which changed the kind and quantity of a hardening accelerator, it became inferior to a color difference.
  • Examples 12 to 22 are all within the scope of the present claims 1 to 4, 6, 8, 9, 12 to 14, 16, 18 and 19, all of Examples 12 to 22 are included in Examples 12 to 22. Some of them are outside of the claims 5, 7, 10, 11, 15, 17, 20 and any of the best modes of the invention described in the specification. Even if the best mode is not maintained, sufficient use as in Examples 1 to 11 can be achieved by devising with the characteristics shown in claims 1 to 4, 6, 8, 9, 12 to 14, 16, 18, and 19. It is likely to become a paint and corrosion resistant member that withstands In fact, some of Examples 12 to 22 should be used as a supplement or reference to the present embodiment.
  • non-leafing aluminum flakes having a large particle diameter in the present invention as a rust preventive pigment, it can be seen that the rust prevention performance can be improved. This is considered to be due to the following reasons.
  • FIG. 2 is explanatory drawing which represents typically the effect
  • a through hole-like defect 6 may occur in the coat film 4 of the rustproof metal member 1.
  • the defect 6 is also caused by chipping, cracking, chipping during use of the anticorrosion metal member 1 or a path when the organic solvent in the coated paint evaporates. Therefore, the occurrence of the defect 6 is an unavoidable phenomenon.
  • the water 5 intrudes into the defect 6 generated in the coat film 4 (and, in some cases, the zinc composite film 3)
  • the zinc contained in the zinc composite film 3 is ionized and sacrificially protected.
  • the rusting action of zinc suppresses the occurrence of rusting of the metal member 2.
  • zinc located immediately below and in the vicinity of the defect in the zinc composite coating is ionized and exhausted.
  • rust such as red rust if the metal member is steel
  • zinc which is not exposed by the defect 6 in the zinc composite coating 3 and is separated from the defect 6 usually remains without being ionized.
  • water 5 is also supplied from the outside to the surface of the coat film 4 which is not illustrated in detail but is not the defect 6. For this reason, it is thought that if the water 5 is supplied to the zinc separated from the defect 6 to ionize it, the anticorrosion action of the zinc can be maintained for a long time.
  • the zinc 30 present in the vicinity of the surface on the coated film 4 side in the zinc composite film 3 is zinc that contributes to sacrificial corrosion protection, and the arrival of water 5 is delayed because the zinc 31 present in the inside away from the surface Is zinc which does not contribute to sacrificial corrosion protection.
  • a passage of the water 5 may be formed in the coat film 4.
  • a slight void is generated at the interface between the non-leafing aluminum flakes 40 and the resin material 41, the interface between the other anticorrosive pigments 42 and the resin material 41, and the interface between the extender pigment 43 and the resin material 41. . Therefore, it is considered that these interfaces can be used as a water passage.
  • the surface areas of the other anticorrosion pigments 42 and the extender pigments 43 are significantly smaller than the surface area of the non-leafing aluminum flakes 40. For this reason, it is considered that the passage of the water 5 in the coat film 4 is mainly constituted by the interface between the non-leafing aluminum flakes 40 and the resin material 41 (hereinafter referred to as the passage interface).
  • the non-leafing aluminum flakes 40 have a major axis larger than the film thickness of the coating for one coat of coating. For this reason, in the case of a coated film formed by applying the coating material once, the non-leafing aluminum flakes 40 are likely to penetrate the coated film in the thickness direction. Even in the case of a coated film formed by two coats of coating paint, non-leafing aluminum flakes 40 dried and fixed while protruding from the coating film in the first coating are adjacent to the second layer non-leafing aluminum flakes 40 in the next coating Or, by passing through, the coated film formed substantially twice by application is penetrated in the thickness direction, or the interface between the first layer coating and the second layer coating makes a passage equivalent to a single application. An interface is considered to occur.
  • the non-leafing aluminum flake 40 has an average particle diameter (long diameter) which is formed by coating once and is larger than the film thickness of the coating for one coating application and can penetrate the coating in the thickness direction,
  • the passage interfaces are connected to each other, and the possibility that the passage interface penetrates the coated film 4 in the thickness direction is increased.
  • a through interface indicated by a white arrow in FIG. 2.
  • a large number of penetration interfaces can be formed, and the zinc in the zinc composite coating 3 can be used without waste, so the anticorrosion performance of the anticorrosion metal member 1 is improved.
  • the rustproofed metal member of the present invention may have one or more of the following features (1) to (10).
  • the value of the average particle diameter D50 of the aluminum flakes not subjected to the leafing process is 1 ⁇ 2 or more of the average thickness of the coated film.
  • the average particle diameter D50 of the aluminum flakes not subjected to leafing processing is in the range of 6 to 22 ⁇ m.
  • the coated film includes an aluminum flake which is fixed by drying so as to penetrate the coated film in the thickness direction and which is not subjected to leafing processing.
  • the aluminum flakes not subjected to the leafing process are contained in an amount of 2.0 to 10% by mass with respect to 100% by mass of the coated film.
  • the resin material is at least one selected from an epoxy resin, a phenol resin, and an acrylic resin.
  • the resin material includes the epoxy resin and the resol-type phenol resin as the phenol resin in a mass ratio of 12: 1 to 2: 1.
  • the coated paint further contains an imidazole-based curing accelerator.
  • the organic solvent is An aromatic solvent comprising at least one selected from toluene, xylene, ethylbenzene and phenol; An alcohol solvent comprising at least one selected from ethylene glycol monobutyl ether, butanol, ethanol and methanol; And at least one ketone solvent selected from at least one ketone solvent selected from methyl ethyl ketone and methyl butyl ketone.
  • the coated film comprises 5 to 18% by mass of 24 to 40% by mass of the resin material, 2 to 10% by mass of aluminum flakes not subjected to the leafing process, and 100 to 100% by mass of the coated film. And an anti-corrosive pigment other than the aluminum flakes not subjected to the leafing process, and 30 to 57% by mass of the extender pigment.
  • the pencil hardness of the coated film is F to B.
  • the coated paint of the present invention may also have one or more of the following features (11) to (18).
  • the value of the average particle diameter D50 of the aluminum flakes not subjected to the leafing process is 1/2 or more of the average thickness of the coated film to be formed.
  • the average particle diameter D50 of the aluminum flakes not subjected to leafing processing is in the range of 6 to 22 ⁇ m.
  • the aluminum flakes not subjected to the leafing process are contained in an amount of 2 to 10 parts by mass with respect to 100 parts by mass of the dry solid content of the coated paint.
  • the resin material is at least one selected from an epoxy resin, a phenol resin, and an acrylic resin.
  • the resin material includes the epoxy resin and the resol-type phenol resin as the phenol resin in a mass ratio of 12: 1 to 2: 1.
  • the organic solvent is An aromatic solvent comprising at least one selected from toluene, xylene, ethylbenzene and phenol; An alcohol solvent comprising at least one selected from ethylene glycol monobutyl ether, butanol, ethanol and methanol; And at least one ketone solvent selected from at least one ketone solvent selected from methyl ethyl ketone and methyl butyl ketone.
  • Antirust metal member 2 Metal member 3: Zinc composite coating 30: Zinc contributing to sacrificial corrosion (broken line) 31: Zinc that can not contribute to sacrificial protection because water does not reach (solid line) 4: Coated film 40: Non-leafing aluminum flakes 41: Resin material 42: Anti-corrosive pigment other than non-leafing aluminum flakes 43: Constitutional pigment 5: Water 6: Defect of coated film

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JP2021195500A (ja) * 2020-06-18 2021-12-27 大日本塗料株式会社 塗料組成物及び塗膜
WO2022109651A3 (en) * 2020-11-30 2024-04-18 Ppg Industries Australia Pty Ltd Anticorrosive coating composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863516A (en) * 1987-01-23 1989-09-05 Sermatech International, Inc. Coating composition
JPH06146005A (ja) 1992-11-11 1994-05-27 Tougou Seisakusho:Kk 金属の防錆構造
JPH09317832A (ja) * 1996-05-31 1997-12-12 Tsubakimoto Chain Co 防食性チェーン用部品
JP2002053837A (ja) * 2000-08-09 2002-02-19 Asmo Co Ltd 接着剤組成物、組立品及びモータ
JP2004356328A (ja) 2003-05-28 2004-12-16 Neomax Co Ltd 耐食性希土類系永久磁石およびその製造方法
US20040265092A1 (en) * 2003-06-30 2004-12-30 Lat Geronimo E. Partially coated fastener assembly and method for coating
JP2009522388A (ja) * 2006-01-02 2009-06-11 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 耐熱性コーティング

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4005254A (en) * 1974-10-29 1977-01-25 General Electric Company Pressureless cure system for chemically cross-linking ethylene containing polymers, and product formed thereby
US4190686A (en) 1978-08-04 1980-02-26 Muis Louis H Protective composition and method
US5066540A (en) 1987-01-23 1991-11-19 Sermatech International, Inc. Flake materials in coating compositions
JPH02263633A (ja) * 1989-04-04 1990-10-26 Nippon Steel Corp プレス加工性及びスポット溶接性に優れた高耐食性着色薄膜塗装鋼板
US6335057B1 (en) * 1997-07-25 2002-01-01 Kansai Paint Co., Ltd. Metallic multilayer coating films formation process
JP4350182B2 (ja) * 1998-10-26 2009-10-21 中国塗料株式会社 防食塗料組成物、防食塗膜および金属基材表面の防食方法
US6599965B2 (en) * 2000-06-22 2003-07-29 Basf Corporation Coating composition for metallic substrates
US6872767B1 (en) 2002-11-14 2005-03-29 Rust Bullett, Llc Method of protecting surfaces with aluminum flaked composition
US20040249044A1 (en) * 2003-02-18 2004-12-09 Tuan Nguyenquang High temperature resistant coating composition
CN100537054C (zh) 2004-03-29 2009-09-09 日本涂料株式会社 光亮性涂膜形成方法和光亮性涂装件
ES2589804T3 (es) 2006-01-02 2016-11-16 Akzo Nobel Coatings International Bv Revestimiento resistente al calor
KR101314011B1 (ko) * 2006-12-29 2013-10-01 주식회사 케이씨씨 선박용 방식 도료 조성물
US8007923B2 (en) * 2007-09-07 2011-08-30 Togo Seisakusyo Corporation Metallic member being subjected to rust-preventive treatment
EP2465843A1 (de) * 2010-12-17 2012-06-20 Sika Technology AG Polyamine mit sekundären aliphatischen Aminogruppen
JP5572875B2 (ja) 2011-12-06 2014-08-20 ユケン工業株式会社 防錆皮膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863516A (en) * 1987-01-23 1989-09-05 Sermatech International, Inc. Coating composition
JPH06146005A (ja) 1992-11-11 1994-05-27 Tougou Seisakusho:Kk 金属の防錆構造
JPH09317832A (ja) * 1996-05-31 1997-12-12 Tsubakimoto Chain Co 防食性チェーン用部品
JP2002053837A (ja) * 2000-08-09 2002-02-19 Asmo Co Ltd 接着剤組成物、組立品及びモータ
JP2004356328A (ja) 2003-05-28 2004-12-16 Neomax Co Ltd 耐食性希土類系永久磁石およびその製造方法
US20040265092A1 (en) * 2003-06-30 2004-12-30 Lat Geronimo E. Partially coated fastener assembly and method for coating
JP2009522388A (ja) * 2006-01-02 2009-06-11 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 耐熱性コーティング

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3748036A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021195500A (ja) * 2020-06-18 2021-12-27 大日本塗料株式会社 塗料組成物及び塗膜
WO2022109651A3 (en) * 2020-11-30 2024-04-18 Ppg Industries Australia Pty Ltd Anticorrosive coating composition

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