WO2017145201A1 - Tôle métallique plaquée revêtue - Google Patents

Tôle métallique plaquée revêtue Download PDF

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Publication number
WO2017145201A1
WO2017145201A1 PCT/JP2016/001510 JP2016001510W WO2017145201A1 WO 2017145201 A1 WO2017145201 A1 WO 2017145201A1 JP 2016001510 W JP2016001510 W JP 2016001510W WO 2017145201 A1 WO2017145201 A1 WO 2017145201A1
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WIPO (PCT)
Prior art keywords
film
coating
inorganic
plated steel
plated
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Ceased
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PCT/JP2016/001510
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English (en)
Japanese (ja)
Inventor
泰載 藤本
原　丈人
上田　耕一郎
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Nippon Steel Nisshin Co Ltd
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Nisshin Steel Co Ltd
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Publication of WO2017145201A1 publication Critical patent/WO2017145201A1/fr
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    • 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
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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

Definitions

  • the present invention relates to a coated plated metal plate.
  • the surface of the plated layer is generally cleaned and activated by applying a degreasing process such as alkaline degreasing and pickling immediately before coating. Then, the repelling of the subsequent coating solution, for example, the chemical conversion solution is suppressed.
  • a degreasing process such as alkaline degreasing and pickling immediately before coating.
  • an inorganic chemical conversion treatment film is produced by applying an inorganic chemical conversion treatment liquid to the adsorption layer
  • the organic part of the organic inhibitor in the adsorption layer may be oriented on the surface of the adsorption layer.
  • the wettability of the above-mentioned treatment liquid before painting of the coated metal plate becomes insufficient, and a uniform chemical conversion treatment film is not produced. For this reason, the adhesion between the plated metal plate and the undercoat film is partially It may be insufficient.
  • polar groups hydroxyl groups, amino groups, etc.
  • the said polar group which contributes may reduce, and there exists a possibility that the adhesiveness between a chemical conversion treatment film and an under_coat_film may fall.
  • the present invention provides, as one means for solving the above problems, a metal plate and a plated metal plate having a plated layer disposed on the surface thereof, and an inorganic acid amine salt disposed on the surface of the plated layer.
  • a coated metal sheet having an inorganic coating, an undercoat coating containing a rust preventive pigment, and an overcoat coating disposed on the undercoat.
  • the present invention it is possible to provide a coated plated metal plate manufactured as a coated plated metal plate having sufficient coating adhesion without degreasing even if the plated metal plate is stored before painting. it can.
  • the coated plated metal plate according to one embodiment of the present invention has a plated metal plate, an inorganic film, an undercoat film, and an overcoat film, which are overlapped in this order.
  • the plated metal plate has a metal plate and a plating layer disposed on the surface thereof.
  • the metal plate can be appropriately determined according to the application of the coated metal plate, and examples thereof include steel plates such as cold rolled steel plates and stainless steel plates, aluminum plates, aluminum alloy plates, and copper plates.
  • Examples of the stainless steel plate include austenitic, martensitic, ferrite, and ferrite / martensite two-phase stainless steel plates. Especially, it is preferable from a viewpoint of intensity
  • the plating metal of the plating layer can be appropriately determined according to the use of the coated plating metal plate as in the case of the metal plate. Examples thereof include zinc (Zn), aluminum (Al), and Zn—Al alloy. And Zn—Al—magnesium (Mg) alloys. Among these, the plating metal of the plating layer is preferably an Al—Zn alloy from the viewpoint of corrosion resistance and appearance.
  • the thickness of the metal plate and the adhesion amount of the plating layer can also be appropriately determined according to the application of the coated metal plate.
  • the thickness of the metal plate is 0.2-2. It may be 0 mm, and the plating adhesion amount may be 20 to 200 g / m 2 on one side.
  • the plated metal plate is preferably a hot dipped metal plate from the viewpoint of corrosion resistance.
  • the hot dip plated metal plate can be manufactured by a known method. For example, an average cooling rate of 10 ° C./second is applied to a metal plate (metal strip) pulled up from a hot dip metal plating bath (bath temperature of 640 ° C. or higher). After cooling to 400 ° C. as described above, it is obtained by heating at 350 to 500 ° C. for 30 minutes or longer (see, for example, JP-A No. 2000-256816).
  • the inorganic film is a layer containing an inorganic acid amine salt.
  • the inorganic film is disposed on the surface of the plating layer. That is, the said inorganic membrane
  • the inorganic acid amine salt may be one kind or more.
  • examples of inorganic acid amine salts include triethanolamine phosphate, hydroxylamine phosphate and zinc nitrite nitrite.
  • the adhesion amount of the inorganic acid amine salt in the inorganic film can be expressed in terms of an anion derived from an inorganic acid or an atom specific thereto.
  • the adhesion amount is preferably 0.1 mg / m 2 or more, and preferably 0.25 mg / m 2 or more from the viewpoint of allowing the chemical conversion coating to adhere with good adhesion and improving coating film adhesion and corrosion resistance. More preferred.
  • coat will crack or cohesive failure will occur and the coating-film adhesiveness of an inorganic membrane
  • the adhesion amount is preferably 50 mg / m 2 or less, more preferably 25 mg / m 2 or less, and 10 mg / m 2 or less. More preferably. From the above viewpoint, the adhesion amount is particularly preferably 0.3 to 2.0 mg / m 2 .
  • the amount of adhesion is determined by measuring the depth at which atoms derived from inorganic acids and nitrogen (N) are present using, for example, a high-frequency glow discharge emission surface analyzer (GDS) or an X-ray photoelectron spectrometer (ESCA). It is possible.
  • GDS glow discharge emission surface analyzer
  • ESA X-ray photoelectron spectrometer
  • the above-mentioned undercoat coating film is a coating film containing a rust preventive pigment.
  • the undercoat film is disposed on the inorganic film, that is, on the surface of the inorganic film, or when there is another layer between the inorganic film and the undercoat film, on the surface of the other layer. .
  • the above-mentioned undercoat coating film has a resin layer constituting the coating film and a rust preventive pigment dispersed therein.
  • the material of the undercoat coating film can be appropriately determined within the range having the above-described configuration.
  • the resin examples include polyester, epoxy resin, and acrylic resin.
  • the number average molecular weight of the resin is preferably 2000 to 30000 from the viewpoint of productivity.
  • the rust preventive pigment may be one kind or more.
  • Examples thereof include zinc phosphate, zinc phosphite, zinc magnesium phosphate, magnesium phosphate, magnesium phosphite, silica, calcium ion exchange silica, phosphoric acid.
  • Zirconium, aluminum dihydrogen triphosphate, zinc oxide, zinc phosphomolybdate, barium metaborate and strontium chromate are included.
  • the content of the rust preventive pigment in the undercoat coating film can be appropriately determined within a range in which the rust preventive effect by the rust preventive pigment can be obtained. It is preferably 15 to 45 parts by mass.
  • the undercoat coating film may further contain other materials than the resin and the rust preventive pigment as long as the effects of the present embodiment are exhibited.
  • examples of such other materials include colored pigments and extender pigments.
  • the coloring pigment include titanium oxide, carbon black, chromium oxide, iron oxide, bengara, titanium yellow, cobalt blue, cobalt green, aniline black, and phthalocyanine blue.
  • the extender pigment include barium sulfate, titanium oxide, silica, and calcium carbonate.
  • the thickness of the undercoat film is preferably 1 to 10 ⁇ m from the viewpoints of corrosion resistance, appearance, workability, cost effectiveness, and the like.
  • the top coat film is disposed on the undercoat film, that is, on the surface of the undercoat film or on the surface of the other layer in the case of having another layer between the undercoat film and the top coat film.
  • a top coat film can be comprised by the resin-made layers which comprise the said coating film.
  • the above resin can be appropriately determined according to the use of the coated metal plate.
  • examples thereof include acrylic resin, polyester, fluorine resin, acrylic-styrene resin, styrene resin, silicone resin, epoxy resin, phenol resin, Urea resins, melamine resins or benzoguanamine resins, resins obtained by urethane modification, silicone modification or epoxy modification of these resins, and resin compositions obtained by mixing two or more of these resins are included.
  • the above-mentioned top coat film may further contain a material other than the above resin as long as the effects of the present embodiment are exhibited.
  • a material other than the above resin examples include curing agents, coloring pigments and extender pigments.
  • the curing agent is a component that binds to the resin and crosslinks between resin molecules.
  • curing agent can be suitably selected according to the kind of said resin, the baking conditions of top coat film, etc.
  • the curing agent include melamine compounds and isocyanate compounds.
  • the melamine compound include an imino group type, a methylol imino group type, a methylol group type or a fully alkyl group type melamine compound.
  • the above-mentioned color pigment can be appropriately selected mainly from the viewpoint of the design properties of the coated plated metal plate.
  • the color pigment include inorganic pigments, composite oxide fired pigments, metallic pigments, and organic pigments.
  • examples of the inorganic pigment include titanium oxide, calcium carbonate, carbon black, iron black, titanium yellow, bengara, bitumen, cobalt blue, cerulean blue, ultramarine blue, cobalt green and molybdenum red.
  • the composite oxide fired pigment is an oxide obtained by firing a metal component.
  • the metal component include CoAl, CoCrAl, CoCrZnMgAl, CoNiZnTi, CoCrZnTi, NiSbTi, CrSbTi, FeCrZnNi, MnSbTi, FeCr, FeCrNi, FeNi, FeCrNiMn, CoCr, Mn, Co, and SnZnTi.
  • Examples of the metallic pigment include Al, resin coating Al and Ni.
  • organic pigment examples include Resol Red B, Brilliant Scarlet G, Pigment Scarlet 3B, Brilliant Carmine 6B, Lake Red C, Lake Red D, Permanent Red 4R, Bordeaux 10B, Fast Yellow G, Fast Yellow 10G, Para Red, Watching Red, benzidine yellow, benzidine orange, bon maroon L, bon maroon M, brilliant fast scarlet, vermilion red, phthalocyanine blow, phthalocyanine green, fast sky blue and aniline black are included.
  • extender pigment examples are the same as those of the undercoat film.
  • the extender pigment in the top coat may be the same as or different from that of the undercoat.
  • the thickness of the top coat is too thin, the desired design properties may not be obtained. If it is too thick, the appearance and workability may be impaired.
  • the thickness is preferably 5 to 30 ⁇ m from the viewpoint of the appearance and workability of the coated metal plate.
  • the painted metal sheet may further include other layers such as other films and coatings as long as the effects of the present embodiment are exhibited.
  • the other layers include a chemical conversion film and an intermediate coating film.
  • the chemical conversion treatment film is disposed on the surface of the inorganic film from the viewpoint of improving the adhesion and corrosion resistance of the coated metal sheet. That is, the chemical conversion treatment film is disposed between the inorganic film and the undercoat film.
  • the chemical conversion coating is a layer containing an active ingredient that contributes to the improvement of the coating adhesion or corrosion resistance.
  • the chemical conversion treatment film may be a chromate film containing hexavalent chromium as the active ingredient, or may be a chromate-free film containing no hexavalent chromium.
  • As the chemical conversion treatment film a known film can be adopted as a chemical conversion treatment film on a coated metal plate.
  • the adhesion amount of the chromate film may be, for example, 5 to 100 mg / m 2 in terms of chromium (Cr).
  • the chromate-free film examples include a Ti—Mo composite film, a fluoroacid-based film, and a phosphate film.
  • the adhesion amount of the Ti—Mo composite film may be, for example, a total adhesion amount in terms of Ti and Mo of 10 to 500 mg / m 2 .
  • the adhesion amount of the fluoroacid-based film may be 3 to 100 mg / m 2 , for example, in terms of fluorine (F) or in terms of all metal elements.
  • the adhesion amount of the phosphate film may be, for example, 0.1 to 5 g / m 2 in terms of P.
  • the intermediate coating film for example, in order to enhance the design properties of the coating plating metal plan by an additive or synergistic effect on the appearance with the top coating film, that is, the surface of the undercoating film, that is, the undercoating film and the above It arrange
  • the intermediate coating film can be composed of a resin layer and may further contain other components depending on the desired effect.
  • the resin and the other components can be appropriately determined from the various materials described in the above-described undercoat and topcoat depending on the application of the coated metal sheet.
  • the thickness of the intermediate coating film is preferably 5 to 40 ⁇ m.
  • the painted metal sheet can be produced by a known method of painted metal sheet except that the inorganic film is formed on the plated layer of the plated metal sheet.
  • the chemical conversion treatment film can be produced by applying and drying a chemical conversion treatment solution that is a mixed solution of the active ingredient and water.
  • the undercoat film, the intermediate coat film and the topcoat film can all be prepared by applying and baking the paint for a paint film further containing the material of the paint film and, if necessary, a solvent. it can.
  • the chemical conversion treatment liquid can be performed by a known method, and examples thereof include a roll coating method, a spin coating method, and a spray method.
  • the drying temperature and drying time of the plated metal plate after coating can be determined as appropriate within the range in which the attached moisture can be evaporated.
  • the drying temperature is 60 to 60 ° C. at the ultimate plate temperature. It is preferably 150 ° C., and the drying time is preferably 2 to 10 seconds.
  • the coating film coating can be applied by a known method, examples of which include a roll coating method, a roller curtain coating method, a curtain flow method, and a spray method.
  • the temperature at which the paint is baked can be appropriately determined according to the type of resin. For example, the ultimate plate temperature is 200 to 260 ° C., and the baking time (the time when the ultimate plate temperature is reached) is 20. ⁇ 100 seconds.
  • the inorganic coating can be produced by applying and drying an aqueous solution of the inorganic acid amine salt (hereinafter also referred to as “inorganic treatment liquid”). That is, the said inorganic membrane
  • Such an inorganic film for example, heats the coating apparatus for the inorganic treatment liquid and the plated metal plate at a position upstream of the take-out device (winding device if steel strip) in the production line for the plated metal plate. It can produce with the manufacturing apparatus of the plating metal plate which has a heating apparatus.
  • FIG. 1 is a diagram schematically illustrating an exemplary configuration of a plating metal plate manufacturing apparatus
  • FIG. 2 is a schematic diagram illustrating an exemplary configuration of a coating plated metal plate manufacturing apparatus.
  • the arrows in the figure indicate the extending (advancing) direction of the steel strip.
  • the plating metal plate manufacturing apparatus includes a heating device 10, a plating bath 20, a water cooling device 25, an inorganic film manufacturing device 30, and a steel strip conveying device as shown in FIG.
  • the steel strip corresponds to the metal plate.
  • the heating device 10 is a device for heating and annealing a steel strip, for example, a known heating device used for heating a steel strip.
  • the plating bath 20 contains the molten metal of the plating layer material.
  • the water cooling device 25 is a device for obtaining a hot dipped metal plate by bringing the metal plate on which the plating layer is formed (when the temperature of the plating layer is lowered to the melting point of the plating metal) into contact with cooling water.
  • the inorganic film manufacturing apparatus 30 wipes the coating apparatus 31 for applying the inorganic treatment liquid onto the surface of the plated layer of the plated steel strip (plated steel strip) and the excess inorganic treatment liquid attached to the plating layer.
  • the coating device 31 is a spray for spraying, for example, an inorganic treatment liquid onto the plating layer.
  • the wiping device 32 is, for example, a wiping roller that absorbs water and rotates in contact with the surface of a plated steel strip.
  • the drying device 33 is a known heating device used for evaporation of moisture on the plating layer.
  • the steel strip conveying device is composed of a plurality of rotatable rollers R that are pivotally supported on a predetermined path in a state where the steel strip and the plated steel strip are stretched.
  • the steel strip extends from the steel strip coil 100 while being supported by the roller R, and reaches the heating device 10.
  • the heating device 10 heats a part of the steel strip in the heating device 10 so as to reach a desired temperature for a desired time.
  • the steel strip is annealed, and the strain in the steel strip is removed.
  • the annealed steel strip further extends toward the plating bath 20. During this time, the steel strip is cooled to a predetermined temperature. Molten metal adheres to both surfaces of the steel strip that has reached the plating bath 20. The steel strip further extends vertically upward, and the molten metal adhering to the surface of the steel strip solidifies by cooling and constitutes a plating layer. The thickness of the plating layer is adjusted by air blown from a blower (not shown). Next, the steel strip having the plating layer extends to the water cooling device 25 and is cooled by the cooling water, for example, by moving in the cooling water.
  • the plated steel strip thus formed further extends toward the inorganic film manufacturing apparatus 30.
  • the drying device 33 evaporates moisture on the surface of the plated steel strip wet with the inorganic treatment liquid, and dries the plated steel strip. Thus, a plated steel strip having the inorganic coating on its surface is produced.
  • the plated steel strip is wound up to become a plated steel strip coil 200.
  • Plated steel strip coils are stored indoors or outdoors for a period of several days to a month, for example, for a period of several days, after appropriate protection such as coating with a coating material such as a film or cover. Is done.
  • the plated steel strip having the inorganic coating is painted with a coated plated metal plate manufacturing apparatus shown in FIG.
  • the device for manufacturing a coated metal sheet includes a water washing device 40, a chemical conversion treatment device 50, an undercoating device 60, an upper coating device 70, and a steel strip conveying device.
  • the water washing device 40 has a water spraying device 41 and a water removing device 42.
  • the water spraying device 41 is a device for spraying water on the surface of the plated steel strip, and is, for example, a spray.
  • the water removing device 42 is a device for removing water adhering to the surface of the plated steel strip from the surface, for example, an air spraying device (air knife).
  • the chemical conversion treatment apparatus 50 can be configured in the same manner as the inorganic film production apparatus 30.
  • the chemical conversion treatment device 50 includes a chemical conversion treatment liquid coating device 51 and a drying device 52.
  • the chemical conversion liquid coating apparatus 51 includes a coating apparatus for applying the chemical conversion liquid to the surface of the inorganic film on the plating layer of the plated steel strip, and a chemical conversion liquid by wiping off the excess chemical conversion liquid adhering to the plating layer. And a wiping device for adjusting the amount of adhesion.
  • the drying apparatus 52 is an apparatus for drying the chemical conversion treatment liquid adhering to the plating layer with the adjusted adhesion amount to form a chemical conversion treatment film on the surface of the inorganic film.
  • the coating device, the wiping device, and the drying device 52 may be the same as those of the inorganic film manufacturing device.
  • the undercoating device 60 heats the plated steel strip to which the undercoating material has been applied, and the first coating device 61 having a first application roller for applying the undercoating material to the surface of the plated steel strip having the chemical conversion coating.
  • the top coating device 70 is configured in the same manner as the under coating device 60, and a second coating device 71 having a second coating roller for applying the top coating material to the surface of the plated steel strip having the undercoat coating film is applied to the top coating device.
  • the steel strip conveying device can be configured in the same manner as that in the plated metal plate manufacturing device, and is configured by, for example, the roller R described above.
  • the plated steel strip extends from the plated steel strip coil 200 while being supported by the roller R, and reaches the water washing device 40.
  • water is sprayed from the spray onto the surface of the plated steel strip. Wash water remaining on the surface of the plated steel strip is removed from the surface by the ejection of air from the air knife.
  • the washing water may be sufficiently removed from the surface of the plated steel strip, and the water removing device 42 may be a wiping device such as a wiping roller.
  • the plated steel strip washed with water is directly extended to the chemical conversion treatment apparatus 50.
  • the coating device such as the spray described above sprays and applies the chemical conversion treatment solution onto the inorganic film on the surface of the plated steel strip
  • the wiping device such as the wiping roller described above is applied on the plating layer.
  • the excess chemical conversion treatment liquid is removed from the surface of the plating layer, and the drying device 52 evaporates moisture on the surface of the plating steel strip wet with the chemical conversion treatment solution, thereby drying the plating steel strip.
  • a plated steel strip having the chemical conversion coating on its surface is produced.
  • the plated steel strip having the chemical conversion coating is further extended to the undercoating device 60.
  • the first application roller applies the undercoating paint to the surface (chemical conversion treatment film) of the plated steel strip with a predetermined adhesion amount.
  • the first heating device 62 heats the plated steel strip to which the undercoat paint is applied, and dries and solidifies the undercoat paint to be baked on the plated steel strip.
  • a plated steel strip having an undercoat coating is produced.
  • the plated steel strip having the undercoat coating film is further extended to the overcoating device 70.
  • the second coating roller applies the top coating material to the surface of the plated steel strip (undercoating film) with a predetermined adhesion amount.
  • the second heating device 72 heats the plated steel strip to which the top coat is applied, and dries and solidifies the top coat to be baked on the plated steel strip.
  • a coated steel strip having layers from the inorganic coating to the top coating is produced.
  • the coated plated steel strip is further extended and wound up with a protective film supplied on the top coat as necessary, resulting in a coated plated steel strip coil 300.
  • the paint-plated steel strip extends from the paint-plated steel sheet coil to a cutting device and is cut into a desired size.
  • the coating-plated steel strip may be extended to the cutting device as it is without being wound and cut.
  • the above-mentioned plated steel strip can be subjected to chemical conversion treatment after storage without degreasing treatment by pickling or alkali washing.
  • the reason for this is not clear, but the inorganic coating on the surface of the plated steel strip suppresses the decrease in wettability to the chemical conversion solution, and if it is a storage period of about one month, a sufficiently uniform chemical conversion solution can be used in the chemical conversion treatment. This is considered to make it possible to form a film.
  • the said coating plating steel strip since it becomes possible to form all the layers on a plating steel strip sufficiently uniformly, sufficient coating-film adhesiveness is exhibited, without performing the said degreasing process.
  • the coated metal plate includes a metal plate and a plated metal plate having a plated layer disposed on the surface thereof, and an inorganic acid amine salt disposed on the surface of the plated layer.
  • An undercoating film containing a rust preventive pigment, and an overcoating film arranged on the undercoating film Therefore, it can be produced as a coated plated metal plate having sufficient coating film adhesion without degreasing the plated metal plate regardless of whether or not the plated metal plate is in an unpainted state.
  • coat is 0.1 mg / m ⁇ 2 > or more.
  • the fact that the plated metal plate is a plated steel plate is more effective from the viewpoint of improving the strength.
  • the coated metal plate further has a chemical conversion film between the inorganic film and the undercoat film from the viewpoint of improving corrosion resistance and coating film adhesion.
  • the painted metal sheet can be manufactured by omitting a degreasing process before coating during the manufacturing process. Therefore, in the production of the coated metal sheet, the equipment and the consumable agent related to the degreasing process are unnecessary, and the waste liquid process such as the neutralization process of the degreasing process is not necessary. For this reason, in the manufacture of the coated metal sheet having sufficient coating film adhesion, it is possible to reduce the environmental load and further reduce the manufacturing cost.
  • a plated steel plate was prepared by forming a plated layer of 55% Al—Zn alloy on both sides of a cold-rolled steel plate having a thickness of 0.5 mm.
  • the plating adhesion amount on one side of the plated steel sheet is 80 g / m 2 .
  • the chemical conversion treatment liquid 1 is a chemical conversion treatment liquid mainly composed of inorganic components.
  • the chemical conversion liquid 2 is a chemical conversion liquid mainly composed of organic components.
  • undercoat “Fine Tough C 700P Primer” manufactured by Nippon Paint Industrial Coatings Co., Ltd. was prepared and used as an undercoat.
  • the undercoat paint is an epoxy resin primer paint.
  • the plated steel sheet was stored for 10 to 30 days in a constant temperature and humidity room at 25 ° C. and 50% RH.
  • the plated steel sheet stored for 10 days is referred to as an original sheet 1
  • the plated steel sheet stored for 20 days is referred to as an original sheet 2
  • the plated steel sheet stored for 30 days is referred to as an original sheet 3.
  • Each of the original plates 1 to 3 was cleaned by spraying water at 25 ° C. and removing moisture from the surface of the original plate with an air knife.
  • the chemical conversion solution 1 is applied to each of the original plates 1 to 3 with a bar coater so that the adhesion amount in terms of chromium (Cr) is 40 mg / m 2 and heated at a final plate temperature of 100 ° C. for 15 seconds.
  • the film of the chemical conversion liquid 1 was dried on the surface of the plating layer of the plated steel sheet.
  • Undercoating is applied to each of the chemical conversion steel sheets 1 to 3 with a bar coater, and the applied paint is baked on the chemical conversion steel sheet for 30 seconds at a final plate temperature of 200 ° C. An undercoat film was formed. Thus, undercoated steel sheets 1 to 3 were obtained, respectively.
  • a top coat was applied to each of the undercoat steel plates 1 to 3 with a bar coater and baked on the undercoat steel plate at an ultimate plate temperature of 230 ° C. for 40 seconds to form a top coat film having a dry film thickness of 13 ⁇ m on the surface of the undercoat film. .
  • painted steel sheets 1 to 3 were obtained, respectively.
  • the plated steel sheet having the upper inorganic film is stored in a constant temperature and humidity room at 25 ° C. and 50% RH for 10 to 30 days.
  • the plated steel sheet stored for 10 days is the original sheet 4
  • the plated steel sheet stored for 20 days is the original sheet 5, 30 days.
  • the stored plated steel sheet was used as the original sheet 6.
  • coated plated steel plates 4 to 6 were produced in the same manner as the coated plated steel plates 1 to 3 except that the original plates 4 to 6 were used instead of the original plates 1 to 3.
  • the coated plated steel sheets 7 to 9 were produced in the same manner as the coated plated steel sheets 4 to 6 except that the amount of the inorganic treatment liquid deposited was changed from 0.01 mg / m 2 to 0.05 mg / m 2 .
  • Coated galvanized steel sheets 10 and 11 were produced in the same manner as the coated galvanized steel sheets 4 and 6 except that the amount of the inorganic treatment liquid deposited was changed from 0.01 mg / m 2 to 0.1 mg / m 2 .
  • the coated galvanized steel sheets 12 and 13 were manufactured in the same manner as the coated galvanized steel sheets 4 and 6 except that the adhesion amount of the inorganic treatment liquid was changed from 0.01 mg / m 2 to 0.3 mg / m 2 .
  • a coated plated steel sheet 17 was manufactured in the same manner as the coated plated steel sheet 14 except that the chemical conversion liquid 2 was used instead of the chemical conversion liquid 1.
  • a comparative processing liquid is used instead of the inorganic processing liquid, and the amount of the comparative processing liquid in the plated steel sheet is adjusted with a squeeze roll so that the amine conversion adhesion amount is 0.5 mg / m 2, and the ultimate plate temperature is 70.
  • the film of the comparative treatment liquid was dried on the surface of the plating layer of the plating layer steel plate by heating at ° C for 15 seconds. Thus, a plated steel sheet having a layer containing an organic amine on the surface of the plating layer was obtained.
  • a part of the original plate 18 was stored, and a part of the original plate 19 was stored in a constant temperature and humidity chamber at 25 ° C. and 50% RH for 30 days.
  • Each of the coated plated steel sheets 18 and 19 was manufactured in the same manner as the coated plated steel sheet 14 except that the original sheets 18 and 19 were used in place of the original sheet 14.
  • the maximum bulge width refers to (the width at which the invasion depth of the bulge from the cut end surface portion is maximized). “A” when the maximum swelling width Wm is less than 3 mm, “B” when the Wm is 3 mm or more and less than 5 mm, “C” when Wm is 5 mm or more and less than 7 mm, and “D” when Wm is 7 mm or more. As evaluated. If it is “A”, “B” or “C”, there is no practical problem.
  • Table 1 shows the amount of amine adhering to the coated plated steel sheets 1 to 21, the storage period of the plated steel sheets, the type of chemical conversion treatment liquid, and the evaluation results.
  • the coated plated steel sheets 4 to 17 having a layer containing an inorganic acid amine salt on the surface of the plated layer of the plated steel sheet at least the plated steel sheet is stored for 10 days in a normal temperature and humidity environment. After storage, a stable film could be formed by applying the chemical conversion solution.
  • the adhesion amount of inorganic acid amine salt is in the range of 0.1 to 2.0 mg / m 2 , even if the plated steel sheet is stored in a room temperature and humidity environment for 30 days, it is stable by application of a chemical conversion treatment solution after storage. In the range of 0.3 to 2.0 mg / m 2 , it is possible to form a film having further excellent coating film adhesion.
  • coated steel sheets 1 to 3 at least two of coating stability, coating film adhesion and corrosion resistance were insufficient. This is because these coated plated steel sheets do not have the above-mentioned inorganic acid amine salt layer, so that the wettability of the surface of the plated layer with water during storage of the coated plated steel sheet is reduced, and the chemical conversion solution is plated at the time of application. It is thought that the surface of the layer was repelled and the adhesion between the plated steel sheet and the undercoat film became insufficient.
  • the coating property stability and the coating film adhesion are improved. Both the corrosion resistance and the corrosion resistance were sufficient, but after storage in a room temperature and humidity environment for 30 days, the coating stability, coating film adhesion, and corrosion resistance were all insufficient. The reason for this is not clear, but during storage, polar groups that are substantially subjected to interlayer interaction in the chemical conversion treatment film are unevenly distributed on the organic amine layer side. This is thought to be due to the fact that the adhesiveness was reduced and became insufficient.
  • the coated plated metal plate of the present invention exhibits sufficient coating adhesion without degreasing treatment before coating even if the plated metal plate is stored before coating. Therefore, the environmental load in the production of the coated metal plate is reduced, the manufacturing cost is reduced, and further spread of the coated metal plate having sufficient performance is expected.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne une tôle métallique plaquée revêtue comprend : une tôle métallique plaquée ayant une tôle métallique et une couche plaquée disposée sur sa surface ; un revêtement inorganique disposé sur la surface de la couche plaquée ; une pellicule de sous-couche disposée sur le revêtement inorganique ; et une pellicule de revêtement disposée sur la pellicule de sous-couche. Le revêtement inorganique comprend un sel d'amine d'acide inorganique, et la pellicule de sous-couche comprend un pigment antirouille.
PCT/JP2016/001510 2016-02-25 2016-03-16 Tôle métallique plaquée revêtue Ceased WO2017145201A1 (fr)

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JP7299489B2 (ja) * 2019-07-08 2023-06-28 日本製鉄株式会社 化成処理鋼板

Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH10140366A (ja) * 1996-11-12 1998-05-26 Nippon Parkerizing Co Ltd 中温リン酸マンガン化成処理液および化成処理方法
JP2004176173A (ja) * 2002-09-30 2004-06-24 Jfe Steel Kk 環境調和性、摺動部耐塗膜剥離性及び加工部耐食性に優れたプレコート鋼板

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JPS4824135B1 (fr) * 1968-12-20 1973-07-19
NL7403614A (fr) * 1973-04-02 1974-10-04
JPS5039646A (fr) * 1973-08-15 1975-04-11
JPH0249791B2 (ja) * 1982-03-19 1990-10-31 Sumitomo Electric Industries Kinzokubannoshorihoho
JP2003105556A (ja) * 2001-09-25 2003-04-09 Nisshin Kako Kk 耐食性が向上したステンレス鋼成型体
JP4067103B2 (ja) * 2002-12-24 2008-03-26 日本ペイント株式会社 脱脂兼化成処理剤及び表面処理金属
JP2006192717A (ja) * 2005-01-13 2006-07-27 Nippon Steel Corp 表面処理金属，その製造方法および表面処理液
JP5991665B2 (ja) * 2012-05-31 2016-09-14 国立研究開発法人産業技術総合研究所 透明ハイブリッド皮膜とその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10140366A (ja) * 1996-11-12 1998-05-26 Nippon Parkerizing Co Ltd 中温リン酸マンガン化成処理液および化成処理方法
JP2004176173A (ja) * 2002-09-30 2004-06-24 Jfe Steel Kk 環境調和性、摺動部耐塗膜剥離性及び加工部耐食性に優れたプレコート鋼板

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