WO2018186474A1 - Tôle d'acier pré-revêtue ayant une bonne résistance aux rayures et une bonne résistance à l'absorption d'humidité dans un film de revêtement et une excellente résistance à la corrosion de surface d'extrémité - Google Patents

Tôle d'acier pré-revêtue ayant une bonne résistance aux rayures et une bonne résistance à l'absorption d'humidité dans un film de revêtement et une excellente résistance à la corrosion de surface d'extrémité Download PDF

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Publication number
WO2018186474A1
WO2018186474A1 PCT/JP2018/014622 JP2018014622W WO2018186474A1 WO 2018186474 A1 WO2018186474 A1 WO 2018186474A1 JP 2018014622 W JP2018014622 W JP 2018014622W WO 2018186474 A1 WO2018186474 A1 WO 2018186474A1
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coating film
steel sheet
pigment
mass
chromate
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PCT/JP2018/014622
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English (en)
Japanese (ja)
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古川　博康
保明 河村
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新日鐵住金株式会社
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Priority to SG11201908797V priority Critical patent/SG11201908797VA/en
Priority to CN201880023350.6A priority patent/CN110520290A/zh
Priority to JP2019511308A priority patent/JP6760489B2/ja
Priority to KR1020197028487A priority patent/KR20190125377A/ko
Publication of WO2018186474A1 publication Critical patent/WO2018186474A1/fr

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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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/06—Polyethene
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • 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
    • 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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a pre-coated steel sheet that is excellent in red rust corrosion resistance on the end face and has good scratch resistance and moisture absorption resistance of the coating film. More specifically, the present invention is a chromate-free pre-coated steel sheet used in an environment where it gets wet with water, particularly in an outdoor environment exposed to rainwater, for example, in the field of electrical products, architecture, etc. The present invention relates to a chromate-free pre-coated steel sheet having excellent scratch resistance as well as excellent resistance to scratches.
  • Patent Document 1 describes an end face red rust-suppressing precoated steel sheet in which a rust preventive pigment exhibiting a red rust suppressing effect is added to a coating film on at least one side of a plated steel sheet.
  • a rust preventive pigment exhibiting a red rust suppressing effect
  • the end surface of the precoated steel sheet is immersed in water, the rust preventive pigment is eluted from the coating film, and the component protects the end surface, thereby suppressing the occurrence of red rust.
  • Sodium tungstate is given as an example of a practical application that is highly effective as a rust preventive pigment.
  • various rust preventive pigments exhibiting a red rust inhibitory effect have been found.
  • New pre-coated steel sheets have been proposed.
  • Patent Document 2 describing a chromium-free coated steel sheet having excellent red rust corrosion resistance
  • alkali metal phosphates and chlorides and alkaline earth metal hypophosphites have a red rust inhibitory effect. It is described that it can be used as a rust preventive pigment.
  • these rust preventive pigments are highly water-soluble and highly deliquescent. They are common in that they are substances having The coating film containing such a deliquescent rust preventive pigment easily absorbs moisture in a high humidity environment, and the problem that the surface of the coating film becomes wet has been revealed. For example, when using a pre-coated steel sheet as a housing for equipment, if the surface of the coating film becomes wet, sticking a caution sticker or foaming material for improving airtightness to the painted surface with an adhesive There was a problem that the adhesive could not adhere.
  • Patent Document 3 describes a pre-coated steel sheet in which a coating layer (hereinafter referred to as a “water-permeable coating”) that easily transmits water is coated on one surface of a plated steel sheet. This is because water easily penetrates into the film and reaches the steel plate surface of the original plate, so that a couple current is positively generated between the ground metal and the plating on the cut end surface of the steel plate, and the sacrificial anticorrosive effect of zinc makes the end surface It is intended to suppress the occurrence of red rust from.
  • a coating layer hereinafter referred to as a “water-permeable coating”
  • a predetermined amount of pigment is contained in a relatively thin film, and at least a part of the film is a pigment having a relatively large particle diameter, so that moisture from the outside can pass through the coating film to form zinc.
  • a coating designed to easily reach the plating layer has been proposed.
  • the present inventors have developed a precoated steel sheet described in Patent Document 4 as a precoated steel sheet that has solved the problems in the techniques of Patent Documents 1 to 3. This is because the surface of the coating film containing anti-rust pigment effective for preventing red rust on the end face allows liquid water to pass through in order to achieve the effect of the anti-rust pigment. It is a pre-coated steel sheet that is covered with an uppermost layer coating film (water permeable / water vapor impermeable coating film) that does not allow gas water (water vapor) that causes it to permeate.
  • an uppermost layer coating film water permeable / water vapor impermeable coating film
  • Patent Document 4 discloses a water-permeable / water-vapor-impermeable coating provided on a coating film containing an antirust pigment. It is described that the film contains a component such as wax.
  • wax is added to a hydrophilized coating film, and the ratio of the projected area of the wax onto the coating film surface is controlled to exhibit excellent moldability by the wax, and tetraalkoxysilane. It has been proposed to exhibit excellent raindrop resistance improvement by the partial hydrolysis condensate.
  • the end surface corrosion resistance of the steel sheet is not considered.
  • the pre-coated steel sheet of Patent Document 4 not only has excellent moisture absorption to prevent wetting of the coating film surface containing a rust preventive pigment for the development of end face red rust corrosion resistance, but also the scratch resistance of the coating film, In particular, it has been revealed that there are problems that the front and back coating film must have scratch resistance for sliding during transportation and that the coating film must have excellent scratch resistance during molding.
  • the present invention aims to solve this problem.
  • the inventors of the present invention have a water permeability on a coating film (hereinafter referred to as “underlayer coating film”) containing a rust prevention pigment (hereinafter sometimes simply referred to as “rust prevention pigment”) for developing red rust corrosion resistance on the end face.
  • underlayer coating film a coating film
  • rust prevention pigment a rust prevention pigment for developing red rust corrosion resistance on the end face.
  • the wax melts during heating and drying to form the uppermost layer coating film. Since the wax is hydrophobic and has a low surface tension, the melted wax wets and spreads on the surface of the coating film or enters the water permeation path in the coating film to block it. Therefore, when the precoated steel sheet gets wet, water cannot permeate the uppermost coating film, and the elution of the anticorrosive pigment in the lower coating film is hindered, thereby inhibiting the expression of end face red rust corrosion resistance.
  • the inventors continued the study by using a wax having a form that is granular and protrudes from the coating film and is scattered in an island shape after the coating film is formed, rather than a wax type that melts by heating.
  • the present inventors have found that it is possible to improve the slidability in order to ensure the corrosion resistance of the end face and at the same time ensure the scratch resistance.
  • the wax used is granular with an average particle size of 1 to 8 ⁇ m, and the content is 1 to 10% by mass with respect to the dry coating film mass, and a part of the wax protrudes from the coating film surface. It was found that is suitable.
  • the present invention has been completed based on these findings.
  • the pre-coated steel sheet of the present invention thus completed corresponds to a coating film thinner than the water-permeable / water-vapor-impermeable coating film of the pre-coated steel sheet of Patent Document 4 and the above-mentioned granular wax added, and specifically,
  • the summary is as follows.
  • a chromate-free pre-coated steel sheet having a chromate-free chemical conversion treatment layer on both surfaces of a zinc-based plated steel sheet, and a plurality of coating films including at least the uppermost coating film and the lower coating film adjacent thereto.
  • the condition of the top layer coating on one side is as follows: (1) The contact angle with water on the surface of the uppermost layer coating film is 65 to 75 °, (2) The film thickness of the uppermost coating film is 0.5-5 ⁇ m, (3) The uppermost layer coating film contains the first pigment, and the content of the pigment is 15 to 70% by mass with respect to the dry coating film mass; (4) Among the first pigments, the total amount of those having an average primary particle size of 1 ⁇ m or more is 5% by mass or more based on the dry coating mass, and (5) the uppermost coating layer has an average particle size of 1 to 8 ⁇ m.
  • the granular wax is contained in a content of 1 to 10% by mass with respect to the dry coating film mass, and at least a part of the granular wax particles is present in a state of partially protruding from the coating film surface.
  • the lower layer coating adjacent to the uppermost layer coating contains a second pigment which is one or more deliquescent rust preventive pigments effective for preventing red rust on the end face.
  • a chromate-free pre-coated steel sheet [2] The chromate-free precoated steel sheet according to [1], wherein the wax is selected from the group consisting of PTFE wax, polyethylene / PTFE co-dispersed wax, and high-molecular polyethylene wax.
  • the second pigment is selected from the group consisting of tungstates and silicates, alkali metal phosphates and chlorides, and alkaline earth metal hypophosphites.
  • the alkali metal phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium tripolyphosphate, sodium dihydrogen phosphate monohydrate, sodium dihydrogen phosphate diwater
  • the chromate-free precoated steel sheet according to [3] above which is a Japanese product or a mixture thereof.
  • the present invention there is no generation of white rust from the surface of the steel sheet, and it is possible to avoid wetness of the coating film in a high humidity environment while exhibiting the effect of suppressing red rust on the end face. It is possible to use a chromate-free precoated steel sheet having sufficient scratch resistance such as galling and scratch resistance for front and back coating films for sliding during transportation.
  • the chromate-free chemical conversion treatment layer formed on the surface of the zinc-based plated steel sheet and the end face red rust formed on the chromate-free chemical conversion treatment layer In contact with the upper surface of the lower layer coating film on the coating layer (hereinafter referred to as “lower layer coating”) containing a rust preventive pigment (hereinafter also referred to as “second pigment”) for the development of corrosion resistance. And a water-permeable / water vapor-impermeable top layer coating film formed as described above. In the present invention, it is important that the uppermost coating film satisfies the following conditions (1) to (5), particularly (5).
  • the contact angle with water on the surface of the uppermost layer coating film is 65 to 75 °
  • the film thickness of the uppermost coating film is 0.5-5 ⁇ m
  • the uppermost layer coating film contains the first pigment, and the content of the first pigment is 15 to 70% by mass with respect to the dry coating film mass, (4) Among the first pigments, the total amount of those having an average primary particle size of 1 ⁇ m or more is 5% by mass or more with respect to the dry coating mass, and (5) the uppermost coating layer is granular having an average particle size of 1 to 8 ⁇ m.
  • the wax is contained at a content of 1 to 10% by mass with respect to the dry coating film mass, and at least some of the granular wax particles are present in a state of partially protruding from the coating film surface;
  • the lower layer coating film adjacent to the uppermost layer coating film contains a second pigment that is one or more deliquescent rust preventive pigments effective for preventing the occurrence of red rust on the end face. Therefore, in the precoated steel sheet of the present invention, according to this condition, at least a part of the wax particles in the uppermost layer coating film is dispersed and scattered in an island shape in a state of partially protruding from the coating film surface.
  • the rust inhibitor can elute through the top layer coating film, ensuring sufficient red rust corrosion resistance at the end face. Is done.
  • At least a part of the granular wax used in the uppermost coating film of the precoated steel sheet of the present invention partially protrudes from the coating film and is scattered in an island shape after forming the coating film.
  • the particulate wax has a melting point exceeding the heating and drying temperature for forming the coating film, or even when melted during the heating and drying of the coating film, it protrudes from the coating film into an island shape after film formation. Use one having a high melt viscosity to such an extent that the granular form that can be scattered is not lost.
  • the melting point of the wax is preferably over 200 ° C., more preferably over 250 ° C., and even more preferably over 300 ° C.
  • the wax having a melt viscosity that does not lose the granular form even when melted at the time of heating and drying of the coating film is 2000 mPa ⁇ s or more, preferably 2500 mPa ⁇ s or more, more preferably at the temperature at which the coating film is heated and dried. Indicates a viscosity of 3000 mPa ⁇ s or more.
  • waxes examples include polytetrafluoroethylene (PTFE) wax, polyethylene / PTFE co-dispersed wax, and high-molecular polyethylene wax.
  • PTFE polytetrafluoroethylene
  • SST series supplied from Shamrock Technologies (USA) can be mentioned.
  • the granular wax used in the present invention preferably has an average particle diameter of 1 to 8 ⁇ m. It is difficult to obtain a granular wax having an average particle size of less than 1 ⁇ m, and it is difficult to obtain a sufficient protruding height from the coating film surface. An average particle diameter exceeding 8 ⁇ m is not preferable because the wax protrudes greatly from the surface of the coated film after film formation, and the wax is likely to fall off when the coated film is rubbed. A more preferable average particle diameter of the granular wax is 3 to 5 ⁇ m.
  • the height at which the granular wax protrudes from the surface of the uppermost coating film is preferably about 0.1 to 3 ⁇ m. If it is less than 0.1 ⁇ m, it is difficult to obtain slidability due to cracking of the protruding portion, and if it exceeds 3 ⁇ m, the wax is transferred to the mold during the press forming of the steel sheet, and it is necessary to frequently care for the mold.
  • a more preferable protrusion height is 0.5 to 2 ⁇ m.
  • the state of presence of the granular wax in the uppermost layer coating film and the film thickness of the coating film of each layer can be confirmed by embedding a test piece of the precoated steel sheet in a resin, polishing the section, and observing the section of the coating film.
  • the film thickness of the uppermost layer coating film is the average value of the film thicknesses of the portions where no granular wax is present.
  • the content of the particulate wax in the uppermost layer coating film is preferably 1 to 10% by mass with respect to the dry coating film mass. If the amount is less than 1% by mass, the effect of adding the wax is not sufficiently exhibited. If the amount exceeds 10% by mass, the cohesive force of the coating film is lowered and film formation is difficult. Since the uppermost coating film in the present invention contains a larger amount of the first pigment than usual in order to obtain water permeability and water vapor impermeability, the cohesive force is essentially small and a large amount of wax is contained. Addition further reduces the cohesive strength of the coating film, which is particularly inconvenient. A more preferable content of the particulate wax is about 1 to 5% by mass with respect to the dry coating film mass.
  • the precoated steel sheet of the present invention will be further described. It is a chromate-free chemical conversion treatment layer on at least both surfaces of a zinc-based plated steel sheet, a lower coating film formed thereon, and an uppermost layer formed adjacent to the lower coating film.
  • a coating film In these coatings, a chromate-free chemical conversion treatment layer, a lower layer coating, and an uppermost layer coating are formed in this order from the surface side of the galvanized steel sheet, and the uppermost layer coating becomes a lower layer coating.
  • the structure is not limited as long as it is provided adjacent to the upper surface of the lower layer coating film.
  • another coating film may be provided between the chromate-free chemical conversion treatment layer and the lower layer coating film.
  • the primer coating layer may be provided on the chromate-free chemical conversion treatment layer, and a plurality of coatings such as one or more upper coating layers may be provided thereon.
  • the uppermost layer coating on one side satisfies the conditions (1) to (5) above, and the lower layer coating adjacent to the galvanized steel plate side of the uppermost layer coating is effective for end face red rust corrosion resistance.
  • 1 type, or 2 or more types of the 2nd pigment which is a deliquescent rust preventive pigment is contained.
  • the lower layer coating film contains a deliquescent rust preventive pigment.
  • any other coating film positioned below the uppermost layer coating film is the above-mentioned rust prevention coating. It is also possible to contain pigments.
  • the second pigment which is a deliquescent rust preventive pigment effective for end face corrosion resistance, is composed of tungstate and silicate, alkali metal phosphate and chloride, and alkaline earth metal hypophosphite.
  • the 1 type (s) or 2 or more types chosen from a group can be mentioned.
  • the tungstate for example, sodium tungstate, calcium tungstate, ammonium tungstate, lithium tungstate, or magnesium tungstate can be used, or a mixture thereof may be used.
  • the tungstate can be mixed in the coating film by about 6 to 50 wt%. When the amount is less than 6 wt%, the end face red rust corrosion resistance is insufficient. When the amount is more than 50 wt%, tungstate is excessively eluted when the coated film is exposed to a wet environment, Peeling may occur.
  • the tungstate content in the coating is more preferably 7 to 40 wt%, most preferably 10 to 30 wt%.
  • silicate for example, sodium silicate, potassium silicate, or lithium silicate can be used, or a mixture thereof may be used.
  • Silicates can be mixed in the coating film by about 5 to 50 wt%. If it is less than 5 wt%, the end face red rust corrosion resistance is insufficient, and if it exceeds 50 wt%, the silicate is excessively eluted when the film after film formation is exposed to a wet environment, and the film is swollen. Peeling may occur.
  • the silicate content in the coating film is more preferably 7 to 40 wt%, and most preferably 10 to 30 wt%.
  • the tungstate or silicate used in the present invention is a powder at room temperature, and the paint is applied until the maximum particle size becomes 5 to 20 ⁇ m, more preferably about 5 to 10 ⁇ m in consideration of the thickness of the mixed coating film. It is preferable to use it in a dispersed manner.
  • alkali metal phosphates and chlorides, or alkaline earth metal hypophosphites can be used as other rust preventive pigments that exhibit end face red rust corrosion resistance.
  • alkali metal phosphate examples include sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium tripolyphosphate, sodium dihydrogen phosphate monohydrate or sodium dihydrogen phosphate dihydrate. Products may be used, or mixtures thereof may be used.
  • alkali metal chloride for example, sodium chloride can be used.
  • hypophosphite for example, calcium hypophosphite can be used.
  • the preferred content of these anticorrosive pigments in the coating film is 0.5-30 wt%, more preferably 1-20 wt%.
  • the anticorrosive pigment used in the present invention can be any combination of the above-mentioned substances.
  • the constituent components other than the anti-corrosion pigment effective in developing the end face red rust corrosion resistance in the lower layer coating adjacent to the uppermost layer coating may be those used in the coating layer of a normal precoated steel sheet.
  • the lower coating film preferably has a thickness of 2 to 20 ⁇ m. If it is less than 2 ⁇ m, the absolute amount of the added anticorrosive pigment is insufficient and sufficient end face red rust corrosion resistance cannot be obtained. If it exceeds 20 ⁇ m, the effect of end face red rust corrosion resistance is saturated and uneconomical, and at the same time during processing The adhesiveness of is reduced.
  • the film thickness is more preferably 3 to 15 ⁇ m, still more preferably 5 to 10 ⁇ m.
  • the film thickness referred to here is the average film thickness of the coating layer, that is, the average of the distance between the interface between the upper layer and the lower layer of the coating layer. The film thickness can be measured by the following method.
  • a pre-coated steel sheet is embedded and cured in an epoxy resin and polished from the cross-sectional direction, and then the cross-sectional observation of the coating film is performed to measure the distance between the upper and lower interfaces.
  • the cross-sectional microscope observation range is at least 10 mm.
  • the uppermost layer coating film adjacent to the lower layer coating film containing the second pigment is in addition to the above condition (5) of [1], (1)
  • the contact angle of water on the coating surface with water is 65 to 75 °, (2)
  • the film thickness of the coating film is 0.5-5 ⁇ m, (3)
  • the coating film contains the first pigment, and the content of the first pigment is 15 to 70% by mass with respect to the dry coating film mass.
  • the average primary particle size is 1 ⁇ m.
  • the total amount of the above is 5% by mass or more based on the dry coating film mass, It is necessary to satisfy the condition.
  • the “first pigment” refers to the entire pigment for the purpose of coloring or rust prevention, but does not include the deliquescent rust preventive pigment existing in the lower layer.
  • other components such as a binder, a pigment, and a bead, are mentioned as a component which comprises dry coating-film mass (mass in the dry state of a coating film).
  • the film thickness referred to here is the average film thickness of the coating film layer, that is, the average of the distance between the surface of the uppermost coating film layer excluding the protruding portion of the granular wax and the interface between the lower coating film. The film thickness can be combined with the above-mentioned measurement of the film thickness of the lower layer coating film.
  • the protruding pigment surface is defined as the lower layer coating film layer. It is considered as the interface.
  • the contact angle of water on the coating surface with water needs to be 65 to 75 °. If it is less than 65 °, the effect as a barrier layer against water vapor is insufficient, and moisture absorption due to the deliquescent action of the rust preventive pigment in the adjacent lower layer coating film cannot be sufficiently suppressed, and if it exceeds 75 °, it is immersed in water. This is because elution of the rust preventive pigment from the lower layer coating is inhibited, and sufficient end face red rust corrosion resistance cannot be obtained.
  • a test piece cut out in a size of 30 mm ⁇ 60 mm by shearing from the prepared coated steel plate is left for 15 hours in wet test conditions (temperature 49 ° C., relative humidity 90-95%), and then a blower is sufficient. After drying, measure the contact angle with the water of the top layer coating film (water permeable / water vapor impermeable coating film) on the surface provided with the coating film containing anti-rust pigment effective for red rust corrosion resistance at the end face. .
  • a general-purpose contact angle measuring instrument (for example, CA-A type contact angle measuring instrument manufactured by Kyowa Interface Science Co., Ltd.) is used to measure the contact angle with water 30 seconds after dropping water droplets from the microsyringe onto the uppermost coating film. Use to measure.
  • the surface of the uppermost coating film hydrophilic, and to contain a predetermined amount of the first pigment in the relatively thin uppermost coating film, and at least one of them.
  • the part is made of a pigment having a relatively large particle diameter, so that the uppermost layer coating film becomes a barrier layer against water (water vapor) as a gas in contact with the uppermost layer coating film, and the second layer in the adjacent lower layer coating film While suppressing the moisture absorption due to the deliquescent action of the rust preventive pigment, the liquid water in contact with the uppermost coating film can reach the surface of the lower coating film by the capillary action of this coating film. The effect of preventing red rust on the end face by elution of the pigment is enabled.
  • liquid water that reaches the surface of the lower layer coating film containing anti-corrosion pigment does not come into contact with the galvanized layer on the steel sheet surface, thereby avoiding the occurrence of white rust from the steel sheet surface due to zinc dissolution.
  • the uppermost coating film that is water-permeable and water-vapor-impermeable is mainly composed of a binder, a first pigment, and the above-described granular wax, and contains other components as necessary. .
  • the binder is composed of a binder resin as a main component, a curing agent, and other components.
  • the type of binder resin is practically selected according to the performance required as a coated steel sheet, and various resins that have been used in coated steel sheets such as epoxy resins, polyurethane resins, and polyester resins are used. be able to.
  • the contact angle of water on the surface of the uppermost layer coating film needs to be 65 to 75 °, and therefore the contact angle is within this range when the uppermost layer coating film is formed by adding other components.
  • a resin that can be Examples of such a resin include a resin containing a partially hydrolyzed condensate of tetraalkoxysilane using an epoxy resin, a polyurethane resin, or a polyester resin as a base resin.
  • tetraalkoxysilanes examples include commercially available products such as methyl silicate 51, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat), MKC silicate MS51, MS56 (manufactured by Mitsubishi Chemical Corporation), and the like. Further, water and a catalyst may be added to a monomer such as tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane to cause hydrolysis and condensation.
  • Examples of the curing agent combined with the binder resin include melamine resin and polyisocyanate compound. If necessary, a crosslinking catalyst may be blended.
  • the content of the binder component with respect to the dry coating film mass is preferably 30 to 85% by mass.
  • the content of the binder component is excessively large, the content of the first pigment is relatively lowered, and the number of pores that can be used for liquid permeation is insufficient, and the corrosion resistance is reduced. Or coloring in a desired color tone becomes difficult.
  • the content is excessively low, the hardness of the coating film itself is increased and the scratch resistance is improved, but the elongation of the coating film itself is decreased, so that the workability is decreased.
  • a particularly preferable range of the content is 40 to 60% by mass with respect to the dry coating film mass.
  • the kind of the first pigment is not particularly limited except that the kind of the first pigment is not the same as that of the second pigment.
  • anti-corrosion pigments include aluminum tripolyphosphate, phosphoric acid and phosphorous acid Zn, Mg, Al, Ti, Zr, and Ce salts, Ca ion exchanged silica, and oil absorption of 100 to 1000 ml / 100 g, specific surface area of 200 ⁇ 1000m 2 / g, like amorphous silica particles having an average particle size of 2 ⁇ 30 [mu] m is.
  • coloring pigments include inorganic pigments such as zinc oxide, titanium oxide, calcium carbonate, and kaolin, organic pigments such as copper phthalocyanine and toluidine red, and carbon black.
  • the uppermost coating film in the present invention contains a larger amount of the first pigment than usual in order to obtain water permeability and water vapor impermeability.
  • the content of the first pigment is 15 to 70% by mass with respect to the dry coating film mass. If the pigment content is less than 15% by mass, liquid water is difficult to permeate the coating film, so that the elution of the anticorrosive pigment in the lower layer coating film is hindered, and the effect of preventing red rust on the end face is less likely to appear. .
  • the pigment content exceeds 70% by mass, it becomes difficult to satisfy other characteristics required for the precoated steel sheet, such as workability.
  • the total content of pigments having an average primary particle diameter of 1 ⁇ m or more with respect to the dry coating film mass needs to be 5% by mass or more.
  • the presence of a pigment having such a relatively large particle size is important for allowing liquid water to permeate.
  • the upper limit of the total content of the pigment having an average primary particle size of 1 ⁇ m or more with respect to the dry coating mass is not particularly set, but is preferably 70% by mass or less for the reason of maintaining workability after coating.
  • the total content of pigments having an average primary particle size of 1 ⁇ m or more with respect to the dry coating mass is more preferably 5 to 30% by mass, and particularly preferably 5 to 15% by mass.
  • the average primary particle size of the first pigment is preferably smaller than the thickness of the coating film.
  • the average primary particle diameter of the pigment is excessively larger than the thickness of the coating film, there is a concern that the corrosion resistance of the painted surface is lowered.
  • the uppermost layer coating film includes a leveling agent, beads for obtaining irregularities in appearance, conductive powder for improving weldability and electromagnetic wave shielding properties, etc., if necessary.
  • Other components may be contained. However, when the content of these components increases, the original properties of the uppermost layer coating such as the permeability of liquid water and the barrier effect against gaseous water are deteriorated.
  • the total content with respect to the mass is preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the thickness of the uppermost layer coating is 0.5-5 ⁇ m. When the thickness is less than 0.5 ⁇ m, the barrier effect against gaseous water (water vapor) is reduced.
  • the uppermost layer coating film of the present invention contains a larger amount of the first pigment than usual in order to obtain water permeability and water vapor impermeability, the cohesive force is essentially small. This is because when the film thickness is increased, the coating film is liable to cohesive failure without being able to withstand the shearing force caused by rubbing on the surface of the coating film. Fragments of the back surface coating film peeled off by rubbing against the front surface coating film also scratch the front surface coating film, resulting in scratches on both the front and back surfaces.
  • the thickness of the uppermost layer coating film is 1 to 5 ⁇ m, and more preferably less than 1 to 2 ⁇ m.
  • the thickness of the coating film is not less than the average primary particle diameter of the first pigment contained.
  • the coating film used as the uppermost coating film of the present invention is similar to the coating film described in Patent Document 3 as being permeable to water.
  • the role of the water-permeable coating film in Patent Document 3 is that when water as a liquid touches the coating film, water freely passes through the coating film to fill the voids in the coating film, and plating under the coating film Wetting the surface with liquid (water).
  • the lower layer adjacent to the uppermost layer coating film is not a plating layer but a coating layer containing a deliquescent rust preventive pigment, but the role of the coating film to permeate liquid water into the lower layer is described in Patent Literature The same as in 3.
  • the top layer coating film has a role of freely diffusing the deliquescent rust preventive pigment that has been impregnated with water into the coating layer and leaching from the lower layer to the water that wets the surface of the precoated steel sheet product. I carry it.
  • the uppermost layer coating film in addition to the above-mentioned role, has another role.
  • the uppermost layer coating layer serves as a barrier layer and suppresses moisture absorption of the deliquescent rust preventive pigment contained in the lower layer. is there.
  • the lower layer adjacent to the uppermost layer coating film is not a plating layer but a coating layer containing a deliquescent rust preventive pigment.
  • the adhesion between the uppermost layer coating and the lower coating layer is better than when the lower layer is a plating layer.
  • the gap that allows water to permeate in the upper layer has a structure in which one end is sealed with the lower layer coating layer, and water can reach the lower layer coating layer by capillary action. Since the lower part of the space
  • the water-permeable coating film of Patent Document 3 has a new function that can be said to have a reverse effect.
  • the water-permeable coating film of Patent Document 3 has a new function that can be said to have a reverse effect.
  • it does not interfere with elution of the deliquescent rust-preventing pigment from the lower layer (conventional function), and does not easily elution when gaseous water touches it. (New function).
  • the coating film (including all coating films on the opposite surface) can be formed from a common material used for the production of chromate-free precoated steel sheets.
  • all the coating films on both sides can be easily formed by ordinary production equipment and production methods, and they need not be described in detail here.
  • a zinc-based plated steel sheet is used as the steel sheet that is the base material of the precoated steel sheet of the present invention.
  • the galvanized steel sheet for example, any one such as hot dip galvanized steel sheet, electrogalvanized steel sheet, Al-galvanized steel sheet, Al-Mg-Si-galvanized steel sheet can be used.
  • the improvement in red rust resistance is particularly remarkable and preferable.
  • a normal chromate-free chemical conversion treatment layer is provided as a pretreatment layer for applying a paint for coating film.
  • the chemical conversion treatment layer can use a film containing two or more of silica, a silane coupling agent, tannin or tannic acid, a zirconium compound, and a titanium compound and a resin.
  • the chemical conversion treatment layer can be formed by dip coating, roll coater coating, ringer roll coating, brush coating, spray coating or the like.
  • a pre-coated steel sheet as a product is generally a surface on the outer side of the finished product that meets the design requirements required by consumers who process it to produce the finished product. Supplied to the customer in the form provided on the surface, the coating on the other side is not required to have the design characteristics required for the coating on the other side, and the coating on the other side. Contains components that do not directly affect the design demanded by customers, such as end face red rust corrosion resistant pigments.
  • the surface on which a sticker for precautionary notes or a foam material for improving airtightness is attached with an adhesive is the other surface that is not touched by human eyes in the final product.
  • the surface with the coating film with the performance required by the customer is the “front surface”, and the surface with the end surface red rust corrosion-resistant pigment-containing coating film and the uppermost coating film adjacent thereto is the “back surface”. I will call it.
  • a general undercoat layer (a polyester / melamine + isocyanate combined curing type FLC687 resin paint (general pigment contained) manufactured by Nippon Fine Coatings Co., Ltd.) ) And dried with hot air at a dry film thickness of 2 ⁇ m and PMT: ultimate plate temperature of 215 ° C.
  • polymer polyester / melamine curable paint FLC8500 resin paint (light beige color) manufactured by Nippon Fine Coatings Co., Ltd.) is dried with hot air at a dry film thickness of 10 ⁇ m, PMT: ultimate plate temperature of 230 ° C. A top coating was formed.
  • the base coating material used for the uppermost coating film formed on the lower coating film (the coating material prior to the addition of wax) is the same as the coating material used for the water-permeable / water vapor-impermeable film described in Patent Document 4 above. Applicable.
  • the base paint indicated as Type I in Table 1 is NKC1200SC Clear (low-contamination imparted (silanol group surface thickening) baking type polyester resin clear type paint made by Nippon Fine Coatings Co., Ltd.) and titania (Ishihara).
  • Other base paints of type II to type IX satisfy the conditions of the uppermost layer coating film of the present application, but are prepared so that various conditions are variously changed.
  • PTFE polytetrafluoroethylene wax (average particle size 2,4,10 ⁇ m, melting point 321 ° C.) of Shamrock Technologies.
  • FLUOROSLIP series polyethylene / PTFE co-dispersed wax (average particle size 4, 6, 13 ⁇ m, melting point 110-130 ° C.) from Shamrock Technologies, TEXTURE series high molecular weight polyethylene wax (average particle size 5,30 ⁇ m, The melting point of the microcrystalline wax and the carnauba wax was 90 ° C. and 80 ° C., respectively.
  • the contact angle of the formed uppermost layer coating film was measured with a CA-A type contact angle measuring instrument manufactured by Kyowa Interface Science Co., Ltd. according to the measurement method described above. As a result, no change was observed in the contact angle with the base coating material when any wax was added.
  • polyester / melamine curable FLC100HQ resin manufactured by Nippon Fine Coatings Co., Ltd. was used as a paint resin for general coating films other than types I to IX.
  • the uppermost layer coating film on the back surface was formed with the film thickness shown in Table 1 as a dry film thickness (PMT: hot air drying at a reaching plate temperature of 230 ° C.).
  • Table 1 shows an overview of the pre-coated steel sheets produced.
  • End face red rust corrosion resistance A distilled water immersion test was conducted. It has been found that the resistance to red rust generated in a short time in a non-electrolyte moist environment can be easily evaluated by a distilled water immersion test. About each precoat steel plate of an Example and a comparative example, 20 test pieces of 10x40mm were each immersed in 40 ml of distilled water put into a petri dish with a diameter of 80 mm, and change of red rust generation on the end face was observed.
  • red rust does not occur at all even if the immersion time in distilled water exceeds 500 hours, and very slight red rust (5 spot rusts with a diameter of 1 mm or less) occurs in 500 hours, but does not occur in 168 hours.
  • red rust (six or more spot rusts with a diameter of 1 mm or less) occurred in 500 hours, but no rust in 168 hours, and rust generated from less than 168 hours was evaluated as x. The results are shown in Table 2.

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Abstract

L'invention concerne une tôle d'acier pré-revêtue de type sans chromate ayant une excellente résistance à la corrosion de surface d'extrémité et une bonne résistance aux rayures et à l'absorption d'humidité dans un film de revêtement, la feuille d'acier pré-revêtue étant caractérisée en ce qu'elle présente, sur les deux surfaces d'une tôle d'acier galvanisée, une couche de traitement de conversion chimique de type sans chromate et une pluralité de films de revêtement, notamment au moins un film de revêtement de couche supérieure et un film de revêtement de sous-couche adjacent à ce dernier, les films de revêtement étant formés sur la couche de traitement de conversion chimique de type sans chromate, le film de revêtement de couche supérieure sur une surface satisfaisant les conditions selon lesquelles (1) l'angle de contact d'une surface de film de revêtement par rapport à l'eau est de 65 à 75°, (2) l'épaisseur du film de revêtement est de 0,5 à 5 µm, (3) le film de revêtement comprend un premier pigment, et la teneur en pigment est de 15 à 70 % en masse de la masse sèche du film de revêtement, (4) la quantité totale de pigment ayant un diamètre de particule primaire moyen de 1 µm ou plus parmi le premier pigment est de 5 % en masse ou plus par rapport à la masse sèche du film de revêtement, et (5) le film de revêtement contenant de 1 à 10 % en masse d'une cire particulaire a un diamètre moyen de particule de 1 à 8 µm par rapport à la masse sèche du film de revêtement, au moins une partie des particules de cire particulaire étant dans un état faisant partiellement saillie depuis la surface de film de revêtement, et le film de revêtement de sous-couche contenant un second pigment qui constitue une ou plusieurs espèces de pigment antirouille déliquescent.
PCT/JP2018/014622 2017-04-05 2018-04-05 Tôle d'acier pré-revêtue ayant une bonne résistance aux rayures et une bonne résistance à l'absorption d'humidité dans un film de revêtement et une excellente résistance à la corrosion de surface d'extrémité WO2018186474A1 (fr)

Priority Applications (4)

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SG11201908797V SG11201908797VA (en) 2017-04-05 2018-04-05 Precoated steel sheet excellent in scratch resistance and moisture absorption resistance of coating and excellent in end face red rust corrosion resistance
CN201880023350.6A CN110520290A (zh) 2017-04-05 2018-04-05 涂膜的耐擦伤性和耐吸湿性良好且端面耐红锈腐蚀性优异的预涂钢板
JP2019511308A JP6760489B2 (ja) 2017-04-05 2018-04-05 塗膜の耐傷付き性及び耐吸湿性が良好で端面赤錆耐食性に優れるプレコート鋼板
KR1020197028487A KR20190125377A (ko) 2017-04-05 2018-04-05 도막의 내흠집성 및 내흡습성이 양호하고 단부면 적청 내식성이 우수한 프리코팅 강판

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CN112175495A (zh) * 2020-09-05 2021-01-05 青岛羚智涂料科技有限责任公司 反应固化密封涂料组合物及其涂覆方法

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JPH09143423A (ja) * 1995-11-21 1997-06-03 Sumitomo Metal Ind Ltd 金属板用塗料組成物及びそれを用いた樹脂被覆金属板とその製造方法
JPH09323376A (ja) * 1996-06-06 1997-12-16 Sumitomo Metal Ind Ltd 着色潤滑処理鋼板およびその製造法
JP2007223556A (ja) * 2006-02-27 2007-09-06 Nisshin Steel Co Ltd シートレール
JP2010083075A (ja) * 2008-10-01 2010-04-15 Sumitomo Metal Ind Ltd 耐端面赤錆性に優れたクロムフリー塗装鋼板
WO2011071175A1 (fr) * 2009-12-07 2011-06-16 新日本製鐵株式会社 Tôle d'acier préenduite exempte de chromate qui présente une excellente résistance à la corrosion de rouille de surfaces d'extrémité
JP2013018263A (ja) * 2011-07-14 2013-01-31 Nippon Steel & Sumitomo Metal Corp 塗装鋼板
JP2016193593A (ja) * 2015-04-01 2016-11-17 新日鐵住金株式会社 耐吸湿性に優れる塗膜を有する端面赤錆耐食性に優れたクロメートフリー型プレコート鋼板

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Publication number Priority date Publication date Assignee Title
JP2009045923A (ja) 2007-07-24 2009-03-05 Sumitomo Metal Ind Ltd 耐端面赤錆性に優れたクロムフリー塗装鋼板

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09143423A (ja) * 1995-11-21 1997-06-03 Sumitomo Metal Ind Ltd 金属板用塗料組成物及びそれを用いた樹脂被覆金属板とその製造方法
JPH09323376A (ja) * 1996-06-06 1997-12-16 Sumitomo Metal Ind Ltd 着色潤滑処理鋼板およびその製造法
JP2007223556A (ja) * 2006-02-27 2007-09-06 Nisshin Steel Co Ltd シートレール
JP2010083075A (ja) * 2008-10-01 2010-04-15 Sumitomo Metal Ind Ltd 耐端面赤錆性に優れたクロムフリー塗装鋼板
WO2011071175A1 (fr) * 2009-12-07 2011-06-16 新日本製鐵株式会社 Tôle d'acier préenduite exempte de chromate qui présente une excellente résistance à la corrosion de rouille de surfaces d'extrémité
JP2013018263A (ja) * 2011-07-14 2013-01-31 Nippon Steel & Sumitomo Metal Corp 塗装鋼板
JP2016193593A (ja) * 2015-04-01 2016-11-17 新日鐵住金株式会社 耐吸湿性に優れる塗膜を有する端面赤錆耐食性に優れたクロメートフリー型プレコート鋼板

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CN110520290A (zh) 2019-11-29
SG10201914074YA (en) 2020-03-30

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