WO2014112544A1 - Tôle en acier galvanisé recouverte d'un film organique et procédé permettant de produire cette dernière - Google Patents

Tôle en acier galvanisé recouverte d'un film organique et procédé permettant de produire cette dernière Download PDF

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Publication number
WO2014112544A1
WO2014112544A1 PCT/JP2014/050638 JP2014050638W WO2014112544A1 WO 2014112544 A1 WO2014112544 A1 WO 2014112544A1 JP 2014050638 W JP2014050638 W JP 2014050638W WO 2014112544 A1 WO2014112544 A1 WO 2014112544A1
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Prior art keywords
organic
steel sheet
beads
film
plated steel
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PCT/JP2014/050638
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English (en)
Japanese (ja)
Inventor
植田　浩平
史生 柴尾
布田　雅裕
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新日鐵住金株式会社
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Priority to JP2014520431A priority Critical patent/JP5644983B1/ja
Publication of WO2014112544A1 publication Critical patent/WO2014112544A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
    • B05D2701/10—Coatings being able to withstand changes in the shape of the substrate or to withstand welding withstanding draw and redraw process, punching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

  • the present invention relates to an organic-coated galvanized steel sheet and a method for producing the same, and more specifically, as a material for home appliances, building materials, civil engineering, machinery, automobiles, furniture, and the like without being subjected to further coating after press molding.
  • the present invention relates to an organic-coated galvanized steel sheet that can be used and a method for producing the same.
  • the organic-coated zinc-based plated steel sheet of the present invention suppresses mold galling and wrinkle generation particularly during press molding, and is excellent in press oil retention.
  • Organic coated galvanized steel sheet that is provided with corrosion resistance, fingerprint resistance, color tone, etc. by coating an organic coating on the surface of the galvanized steel sheet as an organic coated galvanized steel sheet used in home appliances, building materials, automobiles, etc. Has been applied.
  • Such an organic-coated zinc-based plated steel sheet is often used as a material for home appliances, building materials, automobiles and the like without being subjected to further painting after being pressed.
  • press forming of such an organic-coated zinc-based plated steel sheet is performed using a mold having no surface defects in order to prevent appearance defects such as scratches on the surface of the film and galling of the mold. .
  • organic coated galvanized steel sheet that does not easily cause film damage such as wrinkles even when pressed with a mold with a flaw on the surface or a mold with a rough surface, that is, an organic coated galvanized plating with improved scratch resistance. Steel sheets are anxious.
  • Patent Document 1 discloses a technique for forming a clear coating film on the surface of a stainless steel plate.
  • the clear coating film includes a thermosetting resin composition and resin beads.
  • the thermosetting resin composition includes an acrylic resin having a glass transition point of 30 to 90 ° C., and a blocked isocyanate resin and an amino resin that crosslink and cure the acrylic resin.
  • the resin beads are included in the clear coating film at a ratio of 0.5 to 4.0 parts by mass per 100 parts by mass of the thermosetting resin composition.
  • the clear-coated stainless steel sheet produced by this technique is expected to have improved pressure mark resistance and scratch resistance.
  • Patent Document 1 describes that the average particle diameter of resin beads is preferably 0.2 to 3.0 times the film thickness of the clear coating film.
  • the scratch resistance of the clear coated stainless steel plate is improved.
  • the scratch resistance of the organic-coated zinc-based plated steel sheet cannot be sufficiently improved by simply applying this technique to the organic-coated zinc-based plated steel sheet. Specifically, the number of pressure marks generated when the organic-coated zinc-based plated steel sheet was wound, the number of crumbs generated when the steel sheets were rubbed with each other, or when the steel sheet and other materials were rubbed, decreased.
  • the organic coated zinc-based plated steel sheet was pressed with a mold having a flaw on the surface or a mold with a rough surface, the organic coated zinc-based plated steel sheet still had many scratches.
  • the inventors have intensively studied to solve the above problems, and as a result, when the organic coating includes beads that are more than three times the thickness of the organic coating, the scratch resistance of the organic coated zinc-based plated steel sheet is reduced. I found a great improvement. Specifically, when the organic-coated zinc-based plated steel sheet was pressed using a mold having a flaw on the surface or a mold having a rough surface, the number of scratches was greatly reduced.
  • the inventors further studied, and when the zinc-based plated steel sheet was coated using a curtain coater that can apply the paint in a non-contact manner to the zinc-based plated steel sheet to be coated Furthermore, it has been found that large-diameter beads can be mixed into the organic film relatively easily. However, even when a curtain coater is used, it has been difficult to apply beads having a large particle size more than three times the film thickness of the organic coating to a zinc-based plated steel sheet.
  • the inventor pays attention to the physical properties of the organic film and controls the physical properties of the organic film, so that beads having a large particle size more than three times the film thickness of the organic film can be easily applied to the zinc-based plated steel sheet. It has been found that it can be applied.
  • the organic film is preferably composed of a polyester resin having a large number average molecular weight, a small hydroxyl value, and a relatively low glass transition point (that is, relatively soft). did.
  • a resin having a large number average molecular weight and a small hydroxyl value has a molecular structure with few branches and a relatively straight chain, and this linear molecular chain has a relatively long structure.
  • the molecular chain of the resin When the molecular chain of the resin is long, the viscosity of the paint increases, and the large particle size beads in the paint become difficult to settle during coating. For this reason, it becomes easy to mix a large particle size bead in an organic membrane
  • the present invention has been completed based on such knowledge, and the gist of the present invention is as follows.
  • the organic coating is a grain satisfying the condition of ⁇ > 3t, where t is the film thickness and ⁇ is the particle size of the beads.
  • An organic-coated zinc-based plated steel sheet comprising beads having a diameter and having a glass transition point of a resin constituting the beads of greater than 150 ° C.
  • the organic-coated zinc-based plated steel sheet according to any one of 1) to 5) above, which comprises:
  • a production method for obtaining an organic-coated zinc-based plated steel sheet comprising an organic coating having a glass transition point of a resin comprising beads satisfying a particle size and having a glass transition point of 150 ° C. or more.
  • an organic-coated zinc-based plated steel sheet that is resistant to film damage such as wrinkles even when pressed with a mold having a flaw on the surface or a mold having a rough surface (that is, improved scratch resistance). It became possible to do. As a result, operations such as extending the maintenance cycle of the mold and using the mold without maintenance can be performed, and the production cost can be reduced at a press maker than before, and the product can be manufactured at a low cost. In addition, even press manufacturers that do not have mold maintenance technology can use organic-coated galvanized steel sheets, and the applications for these steel sheets have expanded. Furthermore, since the curtain coater is simpler than the roll coater, it can be easily incorporated into the plating line.
  • the present invention can be said to be an industrially highly valuable invention.
  • the organic coated galvanized steel sheet 10 includes a galvanized steel sheet 11 and an organic film 15 covering at least one surface of the galvanized steel sheet 11.
  • the zinc-based plated steel sheet 11 includes a steel sheet 12 and a zinc-based plated layer 13 provided on the surface thereof.
  • the organic film 15 includes beads 14 that satisfy the condition of ⁇ > 3t.
  • t is the film thickness of the organic film 15
  • ⁇ is the particle size (diameter) of the beads 14.
  • the film thickness t of the organic film 15 corresponds to the film thickness in a portion of the organic film 15 whose surface is substantially parallel to the surface of the plating layer 13.
  • ⁇ is 3 t or less
  • the organic-coated galvanized steel sheet 10 is pressed with a rough surface mold or a mold containing wrinkles, wrinkles are likely to enter the surface of the coating. Therefore, beads with ⁇ of 3 t or less are not suitable for this embodiment.
  • the number of beads 14 (that is, beads satisfying the condition of ⁇ > 3t) is not particularly limited. However, when one or more beads 14 are found when observing an arbitrary cross section of the organic coated zinc-based plated steel sheet 10 with a length of 20 mm, it becomes difficult for wrinkles to enter the surface of the coating during press working. Therefore, it is preferable that one or more beads 14 exist in an arbitrary cross section of the organic coated zinc-based plated steel sheet 10 having a length of 20 mm.
  • a preferred example of the method of observing the cross section of the organic coated zinc-based plated steel sheet 10 is as follows. That is, the organic-coated zinc-based plated steel sheet 10 is cut along an arbitrary cross section having a length of 20 mm, and the cross section is embedded in the resin so that the steel sheet is perpendicular to the resin surface. Then, the cross section is polished (this method is also called resin embedding polishing). Then, the cross section is observed with an optical microscope or an electron microscope.
  • the bead can be determined as a bead satisfying the condition of ⁇ > 3t, that is, the bead 14. Therefore, the number of beads 14 can be measured by the above method.
  • An example of a cross-sectional microscopic observation photograph of the organic coated zinc-based plated steel sheet 10 is shown in FIG.
  • the upper limit of the number of beads 14 existing in a cross section having a length of 20 mm varies depending on the particle diameter and film thickness of the beads added to the organic coating 15, and is not particularly defined. It only has to be done. However, if the number of beads 14 is too large, the beads 14 are easily detached from the organic film 15. Therefore, it is preferable to confirm beforehand the number of beads 14 not to fall off from the organic film 15 by experiments or the like.
  • the total number of beads in the cross section (the total number of beads 14 and beads for which ⁇ is 3 t or less) is 10 or more, and the beads 14 are beads in the cross section. More preferably, it is 1.0% or more based on the total number. In this case, film damage is less likely to occur.
  • the bead distribution can be measured by the same method as described above. Further, the distribution of the beads can be adjusted by adjusting the particle size distribution of the beads, the viscosity of the paint, and the condition of stirring the paint before painting. The particle size distribution of the beads can be adjusted by placing the beads on a classifier. The optimum conditions for these parameters are not particularly defined, and the optimum conditions may be found by conducting a test in advance.
  • the preferred range of the film thickness of the organic film 15 is 3 to 20 ⁇ m. It is difficult to stably apply the paint including the beads 14 on the galvanized steel sheet 11 with a thickness of less than 3 ⁇ m using a curtain coater. In addition, when the film thickness of the organic film 15 exceeds 20 ⁇ m, appearance defects (such appearance defects and boiling) are likely to occur due to bumping marks generated during the drying and curing process of the paint. A more preferable range of the film thickness is 5 to 20 ⁇ m. When the film thickness is within this range, the corrosion resistance of the galvanized steel sheet is improved.
  • the glass transition point of beads 14 is greater than 150 ° C.
  • the glass transition point of the beads 14 is preferably 170 to 190 ° C.
  • the melting point of the beads 14 is preferably 250 ° C. or higher.
  • the resin constituting the beads 14 include acrylic resins and polystyrene resins.
  • the upper limit of the particle size of the beads 14 is not particularly defined, and can be appropriately selected as necessary. However, if the particle size of the beads 14 is too large with respect to the film thickness t, the beads 14 are easily detached from the organic film.
  • the detachment of the beads 14 greatly affects the compatibility (for example, adhesion) between the coating film and the beads, it is necessary to evaluate in advance and appropriately select the beads 14 having a particle size that does not detach.
  • the upper limit of the particle size is considered to be about 100 ⁇ m. This is because if it exceeds this, the beads 14 easily fall off from the coating film.
  • the surface of the bead is covered with an organic film 15.
  • coat 15 which covers the surface of a bead is 0.1 micrometer or more.
  • the upper limit of the film thickness of the organic film 15 covering the surface of the bead 14 is not particularly specified, but it is physically difficult to exceed the film thickness of the organic film 15 coated on the galvanized steel sheet 11, so that the zinc film The film thickness of the organic film 15 coated on the plated steel sheet 11 becomes the upper limit value. As a result, film damage is less likely to occur.
  • the organic film paint when the organic film paint is applied to the galvanized steel sheet 11 using the roll coater, the organic film paint on the surface of the beads is scraped off by the roll, so it is very difficult to cover the surface of the beads 14 with the organic film 15. It is difficult to.
  • the curtain coater can apply the organic coating material to the galvanized steel plate 11 without contacting the organic coating material, the bead surface can be covered with the organic coating 15.
  • the film thickness of the organic film 15 on the bead surface can be measured by observing the cross section of the film by the same method as the measurement of the distribution of the beads 14, and the film thickness of the organic film 15 covering the bead surface is the same as that of the organic film 15.
  • the molecular weight and hydroxyl value of the main resin can be adjusted.
  • a resin having a small hydroxyl value is composed of straight-chain molecules having few molecular chain branches. That is, a resin having a small hydroxyl value has a substantially long molecular chain, and therefore easily covers the beads 14.
  • the organic film 15 may contain a coloring pigment in addition to the beads 14. By including the color pigment, design properties can be imparted to the organic film 15, which is preferable.
  • pigments that can be added to the organic film 15 include generally known color pigments such as carbon black as a black pigment, titanium oxide as a white pigment, cadmium red as a red pigment, inorganic red pigments such as silver vermilion, and carmine 6B.
  • Organic soluble azo red pigments such as Lake Red C and Watching Red, Permanent Red, Lake Red 4R, Organic insoluble azo red pigments such as naphthol red, Condensed azo red pigments such as chromoftal red, Yellow lead Inorganic yellow pigments such as yellow iron oxide and cadmium yellow, organic yellow pigments such as disazo yellow, monoazo yellow and condensed azo yellow, inorganic orange pigments such as molybdenum orange, and organic orange pigments such as disazo orange and permanent orange Can be used.
  • the coloring pigment may be a generally known metallic pigment. Examples of metallic pigments include aluminum flakes, nickel flakes, stainless steel flakes, and gold foil.
  • the color pigment may be glass flakes or resin flakes on which a metal such as aluminum is deposited.
  • the coloring pigment may be a generally known pearl-like pigment, for example, mica coated with a metal oxide such as mica, titanium oxide, or iron oxide.
  • the addition amount of the color pigment is not particularly limited, and may be appropriately adjusted according to the design appearance required for the organic-coated zinc-based plated steel sheet 10.
  • the friction coefficient of the surface of the organic film 15 is preferably 0.17 or less. In this case, the scratch resistance of the organic-coated zinc-based plated steel sheet 10 is further improved.
  • Examples of a method for setting the coefficient of friction of the surface of the organic film 15 to 0.17 or less include a method of adding wax to the organic film 15.
  • the wax may be a generally known wax for paint.
  • Examples of the coating wax include carnauba wax, fluorine wax, paraffin wax, and microcrystalline wax.
  • a preferable addition amount of the wax is not particularly limited because it varies depending on the kind of the main resin constituting the organic film 15 and the like. That is, the friction coefficient of the surface of the organic film 15 may be set to 0.17 or less by adjusting the amount of wax added according to the type of the main resin constituting the organic film 15 and the like.
  • the main resin of the organic film 15 is preferably a resin obtained by crosslinking a polyester resin with an amino resin.
  • the main resin of this embodiment means resin with the largest mass% with respect to the total mass of the organic membrane
  • the number average molecular weight of the polyester resin is preferably 13,000 to 30,000, the hydroxyl value is preferably 10 KOH mg / g or less, and the glass transition point (hereinafter referred to as Tg) is 3 to 50 ° C. Preferably there is. When these conditions are satisfied, when the paint containing the beads 14 is curtain-coated on the galvanized steel sheet 11, the beads 14 are easily mixed in the paint layer, and the beads 14 are detached from the paint layer even after the mixing. Hateful.
  • the paint curtain may be difficult to form during curtain coating.
  • the coating containing the beads 14 can be applied to the galvanized steel sheet 11 by another coating method, the beads 14 are likely to be detached from the organic coating 15 during the press working of the organic coated galvanized steel sheet 10. For this reason, there exists a possibility that a wrinkle may enter into the organic membrane
  • the number average molecular weight of the polyester resin is more than 30,000, the viscosity of the paint is too high, and as a result, there is a possibility that the coating becomes difficult or cannot be performed.
  • the hydroxyl value of the polyester resin exceeds 10 KOHmg / g, the number average molecular weight of the polyester resin is small or the polyester resin becomes branched. This may make it difficult to form a paint curtain during curtain coating.
  • the paint containing the beads 14 can be applied to the galvanized steel sheet 11 by another coating method, the beads 14 are likely to be detached from the organic film 15 when the organic coated galvanized steel sheet 10 is pressed. For this reason, there exists a possibility that a wrinkle may enter into the organic membrane
  • the polyester resin used as the main resin of the organic film 15 may be a generally known polyester resin.
  • polyester resins examples include “Byron TM ” (registered trademark of Toyobo Co., Ltd.) manufactured by Toyobo Co., Ltd. and “Desmophen TM ” (registered trademark of Sumika Bayer Urethane Co., Ltd.) manufactured by Sumika Bayer Urethane Co., Ltd. It is done.
  • the main resin of the organic film 15 may be a mixture of these polyester resins.
  • the glass transition point of the polyester resin is preferably 3 to 20 ° C., and more preferably 3 to 10 ° C.
  • the glass transition point is a value within these ranges, the organic film 15 becomes soft, so that even if the organic film 15 is damaged, the damage can be easily repaired.
  • the glass transition point of the polyester resin may be 40 to 50 ° C. In this case, since the organic film 15 is hardened, not only is the scratch itself difficult to be scratched, but also the workability and corrosion resistance of the galvanized steel sheet 11 are improved.
  • the hydroxyl value of the polyester resin is preferably 5 KOHmg / g or less although there is a measurement limit.
  • the polyester resin is closer to a straight chain, it becomes easier to form a paint curtain. Therefore, it becomes easier to form the organic film 15. Furthermore, there is an advantage that it is easy to cover the beads 14 with the organic film 15.
  • the press formability of the organic-coated zinc-based plated steel sheet 10 is more excellent.
  • the addition amount of the amino resin is less than 15 parts by mass, the degree of cross-linking of the organic film 15 becomes low, so that the organic film 15 becomes very soft. For this reason, the beads 14 are easily detached from the organic coating 15 when the organic coated zinc-based plated steel sheet 10 is pressed. As a result, wrinkles may enter the organic film 15.
  • the amino resin that can be added to the organic film 15 may be a generally known amino resin.
  • Examples of amino resins that can be added to the organic film 15 include fully alkyl methylated melamine, imino group methylated melamine, methylol melamine, methylol group methylated melamine, fully alkyl mixed etherified melamine, and methylol group.
  • Melamine resins such as type mixed etherified melamine and imino group type mixed etherified melamine, butylated melamine, benzoguanamine resin, amino resin and the like. More specific examples of possible amino resin added to the organic film 15, commercially available, for example, CYTEC Co., Ltd. Amino resin "CYMEL TM Series” and “MYCOAT TM Series”, manufactured by Mitsui Chemicals, Inc. of amino system resin "U-VAN TM Series", DIC Co., Ltd. "Super BECKAMIN TM Series” and the like.
  • the number of layers of the organic film 15 is not particularly limited, but it is preferable to form only one layer from the viewpoint of cost. Since the organic film 15 of the present embodiment includes beads 14 having a particle size satisfying the condition of ⁇ > 3t and a glass transition point of greater than 150 ° C., even when only one layer of the organic film 15 is formed. The scratch resistance of the organic coated zinc-based plated steel sheet 10 can be greatly improved.
  • a chemical conversion treatment is performed between the zinc-based plating layer 13 and the organic film 15 of the organic-coated zinc-based plated steel sheet 10.
  • the organic coating 15 is difficult to peel off during press forming of the organic coated zinc-based plated steel sheet 10.
  • the type of chemical conversion treatment is not particularly limited. Examples of the chemical conversion treatment that can be carried out in the present embodiment include generally known chemical conversion treatments for galvanized steel sheets.
  • the chemical conversion treatment of the present embodiment may be zinc phosphate chemical conversion treatment, coating chromate treatment, electrolytic chromic acid treatment, reaction chromate treatment, chromate-free chemical conversion treatment, or the like.
  • chromate-free chemical conversion treatment a method of treating a zinc-based plating layer with an aqueous solution containing a silane coupling agent, a zirconium compound, a titanium compound, tannin or tannic acid, a resin, silica, or the like is known.
  • the chemical conversion treatment of this embodiment is disclosed in JP-A-53-9238, JP-A-9-241576, JP-A-2001-89868, JP-A-2001-316845, JP-A-2002-60959, Known chemical conversion treatments described in JP-A-2002-38280, JP-A-2002-266081, JP-A-2003-253464, etc. may be used.
  • a treatment solution for performing these chemical conversion treatments a commercially available chemical treatment solution, for example, chromate treatment solution “ZM-1300AN” manufactured by Nihon Parkerizing Co., Ltd., chromate-free chemical treatment solution “CT-E300N” produced by Nihon Parkerizing Co., Ltd. And a trivalent chromium-based chemical conversion treatment solution “Surfcoat® NRC1000” manufactured by Nippon Paint Co., Ltd.
  • the paint layer containing the beads 14 is applied to the galvanized steel sheet 11 with a curtain coater and then the paint layer is dried and baked. Thereby, the beads 14 are easily mixed into the organic film 15.
  • a coating apparatus other than the curtain coater, for example, a roll coater is not suitable for this embodiment because the beads 14 can hardly be mixed into the organic film 15.
  • the type of galvanized steel sheet 11 is not particularly limited.
  • the galvanized steel sheet 11 is generally known such as a hot dip galvanized steel sheet, an electrogalvanized steel sheet, a zinc-nickel alloy plated steel sheet, an alloyed hot dip galvanized steel sheet, an aluminum-zinc alloy plated steel sheet, a zinc-aluminum-magnesium alloy plated steel sheet. Any zinc-based plated steel sheet may be used.
  • the organic film 15 may be formed on both sides of the galvanized steel sheet 11 or only on one side.
  • a generally known back coating film, thin film organic film, inorganic chemical conversion film, etc. may be formed on the other surface of the galvanized steel sheet 11. .
  • corrosion of the other surface of the galvanized steel sheet 11 is suppressed.
  • the coefficient of friction of the film (back surface film) formed on the other surface of the galvanized steel sheet 11 is preferably 0.17 or less. In this case, since the slidability at the time of press molding of the organic coated galvanized steel sheet 10 is enhanced, the press moldability of the organic coated galvanized steel sheet 10 is improved.
  • polyester resin As a polyester resin, “Byron TM 103” which is an amorphous polyester resin manufactured by Toyobo Co., Ltd. (Tg: 47 ° C., number average molecular weight: 23000, hydroxyl value: 5 KOH mg / g [described as B-103 in Table 1) ), “Byron TM 630” which is an amorphous polyester resin manufactured by Toyobo Co., Ltd.
  • Byron TM GK130 Tg: 15 ° C., number average molecular weight: 7000, hydroxyl value: 19 KOHmg / g [Table 1] Some are described as B-GK130]
  • “Byron TM GK180” an amorphous polyester resin manufactured by Toyobo Co., Ltd. (Tg: 0 ° C., number average molecular weight: 10,000, hydroxyl value: 23 KOH mg / g [in Table 1) Is described as B-GK180]
  • Byron TM 230 which is an amorphous polyester resin manufactured by Toyobo Co., Ltd.
  • polyester resins are in the form of pellets or sheets, they are used by dissolving them in an organic solvent (a mixture of cyclohexanone and Solvesso 150 (trade name) at a mass ratio of 1: 1).
  • organic solvent a mixture of cyclohexanone and Solvesso 150 (trade name) at a mass ratio of 1: 1).
  • CYMEL TM 303 which is a fully alkyl methylated melamine resin manufactured by CYTEC was added as an amino resin to the polyester resin dissolved in the solvent. Furthermore, by adding 0.5% by mass of the catalyst “CYCAT TM 600” manufactured by CYTEC as an acidic catalyst to the polyester resin and melamine resin dissolved in the solvent with respect to the solid content (total of polyester resin and melamine resin). A clear paint was prepared.
  • coloring pigments black pigment, white pigment, metallic pigment
  • metallic pigments Aluminum flakes manufactured by Toyo Aluminum Co., Ltd. were used.
  • PMMA beads having a maximum particle size of 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 30 ⁇ m, 55 ⁇ m, and 65 ⁇ m were prepared by classifying fine particles of polymethyl methacrylate (PMMA).
  • PS beads having a maximum particle size of 30 ⁇ m were prepared by classifying polystyrene (PS) fine particle powder.
  • each bead was added to the base coating material at a ratio of 3 parts by mass with respect to 100 parts by mass of the total solid content of the base coating material (total solid content of polyester resin, melamine resin, and pigment).
  • the beads used in Example 1 all had a glass transition point of 190 ° C. and a melting point of 250 ° C.
  • microcrystalline wax was added as necessary.
  • the amount of microcrystalline wax added was the value shown in Table 1 with respect to 100 parts by mass of the total solid content of the base paint (total solid content of the polyester resin, melamine resin and pigment).
  • an organic solvent (a mixture of cyclohexanone and Solvesso 150 (trade name) at a mass ratio of 1: 1) was added to the coating material prepared above to make the total solid content concentration 30% by mass. Thereby, an organic film paint was produced.
  • Table 1 shows the organic coating materials that were produced.
  • the plating adhesion amount of EG was 20 g / m 2 on one side (the same adhesion amount on both surfaces), and the plating adhesion amount on GI and ZM was 60 g / m 2 on one side (the same adhesion amount on both surfaces).
  • Oil was not applied to the zinc-based plated steel sheet, and the zinc-based plated steel sheet was used as it was.
  • Some of the zinc-plated steel sheets were subjected to chemical conversion treatment. Specifically, the chemical conversion treatment liquid was applied on both surfaces of the zinc-based plated steel sheet with a roll coater so as to adhere to the zinc-based plated steel sheet with a surface density of a total solid content of 200 mg / m 2 .
  • the chemical conversion solution was dried in a hot air oven. The set temperature of the hot air oven was set to 60 ° C. as the ultimate plate temperature of the steel plate.
  • the organic film paint shown in Table 1 was applied to one surface of all zinc-based plated steel sheets using a curtain coater or a roll coater, and the back film paint was applied to the other surface using a roll coater. Subsequently, each paint was dried (baked) in a hot air oven. Here, the ultimate plate temperature during drying was 230 ° C. The time from the start of drying to the time when the plate temperature reached 230 ° C. was 30 seconds. Water was sprayed on the steel plate after drying, and then the steel plate was water-cooled to obtain a test material. The film thickness (dry film thickness) of the organic film was as shown in Table 2, and the film thickness (dry film thickness) of the back film was 0.8 ⁇ m.
  • film thicknesses were obtained by adjusting the paint discharge flow rate of the curtain coater, the peripheral speed of the roll of the roll coater, the nip pressure between rolls, and the solid content concentration of the paint.
  • the film thickness was measured with an electromagnetic film thickness meter after the galvanized steel sheet was dried.
  • a back film coating material was prepared by adding the same wax as that used in the organic coating material to “FL100HQ” manufactured by Nippon Fine Coatings Co., Ltd., which is a commercially available polyester-based coating material. The amount of wax added was adjusted so that the friction coefficient ⁇ of the back film was 0.1. The color of the back coating film was clear.
  • Table 2 shows the prepared specimens (samples).
  • a sample in which the film is not peeled off at all, or a sample in which no crack is observed even when observed with a 10 ⁇ magnifier, is “VG (very good)”; “G (good)” is a sample in which cracks are observed in the sample, “P (poor)” is a sample in which the film peeling width from the end surface of the molded product is 5 mm or less, or samples in which minute cracks are visually observed.
  • One mold pair 32 has a surface 32a mirror-finished (specifically, Ra of the surface 32a is less than 0.1 ⁇ m).
  • the flat plate sliding test using the mold pair 32 is an operation reproduction test in which the organic-coated galvanized steel sheet 10 is pressed with a mold that does not contain wrinkles.
  • the surface 32a is finished with high roughness (specifically, Ra of the surface 32a is 0.2 to 0.3 ⁇ m).
  • the flat plate sliding test using the mold pair 32 is a reproduction test of an operation in which the organic-coated zinc-based plated steel sheet 10 is pressed with a mold containing a flaw.
  • the observed surface is the surface coated with the organic film (surface).
  • the case where the organic film was not damaged at all was “VG (very good)”, and the case where the film had linear streaks.
  • the evaluation was “G (good)”, “P (poor)” when the film was partially peeled, and “B (bad)” when the film was completely peeled off.
  • Corrosion resistance test A sample for a corrosion resistance test was prepared by cutting the sample into a size of 70 mm in width and 150 mm in length and sealing the whole end face portion with tape. And the salt spray test was implemented by the method as described in JISZ2371. The salt water was sprayed on the surface (surface) having the organic film. The test time was 72 hours.
  • the rust generation area ratio of the surface having the organic film (surface) is evaluated.
  • a rust generation area ratio of 0% is “VG (very good)” and a rust generation area ratio of 5% or less is “G (good)”. ”, 10% or less was evaluated as“ P (poor) ”, and 10% or more was evaluated as“ B (bad) ”.
  • Table 2 shows the evaluation test results.
  • Invention Examples-1 to 6, 10 to 15, 19 to 35, 38 to 39, 41 to 42, 49 to 61 include beads satisfying the condition of ⁇ > 3t. For this reason, even if these invention examples are press-molded using a high-roughness mold, wrinkles and the like are unlikely to enter the organic film. That is, these inventive examples were excellent in press formability.
  • Invention examples in which one or more beads satisfying the condition of ⁇ > 3t were discovered when an arbitrary cross section having a length of 20 mm was observed (Invention Examples 1 to 6, 10 to 15, 19 to 35, 38, 39, 41, 42, 49 to 61) were press-molded using a high-roughness mold, and it was difficult for wrinkles or the like to enter the organic film. Therefore, these invention examples were excellent in press moldability.
  • the film thickness of the organic film covering the beads is a value within the range of 0.1 ⁇ m or more. there were. Therefore, also in this respect, the examples of the present invention were excellent in press formability.
  • the main resin of the organic film is composed of 100 parts by mass of a polyester resin having a number average molecular weight of 13,000 to 30,000, a hydroxyl value of 10 KOH mg / g or less, and a Tg of 3 to 50 ° C., and 15 to 30 parts by mass of an amino resin.
  • a favorable result was obtained when the glass transition point of the main resin of the organic film was 3 to 20 ° C., 3 to 10 ° C., or 40 to 50 ° C.
  • more favorable results were obtained when the hydroxyl value was 5 KOH mg / g or less.
  • a polyester resin having a polyester resin with a number average molecular weight exceeding 30,000 could not be confirmed in this experiment because it was difficult to obtain as a coating resin.
  • the organic coating material containing the polyester resin has a high viscosity, and it is expected that curtain coating using the organic coating material is difficult.
  • the polyester resin When an example of the invention in which the Tg of the polyester resin exceeds 50 ° C. (Examples of Invention-33, 34) is press-molded using a high-roughness mold, the polyester resin has a Tg of 50 ° C. or less, which is more organic. It was easy to get wrinkles in the film.
  • Invention Examples (Invention Examples 5 and 14) in which the amino resin is less than 15 parts by mass, and Invention Examples (Invention Examples 4 and 13) in which the amino resin exceeds 30 parts by mass are used in a high roughness mold. In the case of press molding, wrinkles or the like tended to easily enter the organic film as compared with the invention examples in which the amino resin content was 15 to 30 parts by mass.
  • inventive examples When the inventive example in which the chemical conversion treatment was performed between the zinc-based plating layer and the organic coating was press-molded using a high-roughness mold, wrinkles and the like were difficult to enter the organic coating. Therefore, these invention examples were excellent in press moldability.
  • inventive examples not subjected to chemical conversion treatment (Invention Examples-41, 42) were press-molded using a high-roughness mold, and inventive examples prepared under the same conditions except that chemical conversion treatment was performed ( It was easier for wrinkles or the like to enter the organic film than Inventive Examples-1 and 10).
  • Example 2 was performed in order to investigate the correlation between the glass transition point of the beads and the scratch resistance of the organic-coated zinc-based plated steel sheet. Specifically, the beads used in Example 1 of the present invention described above were changed to beads having glass transition points of 200 ° C., 170 ° C., 155 ° C., 150 ° C., and 140 ° C. (melting points were all 250 ° C.) The sample material was produced by the same method as the production method of Invention Example 1.
  • These beads are made of polymethyl methacrylate (PMMA) fine particle powder having a glass transition point of 200 ° C., 170 ° C., 155 ° C., 150 ° C., and 140 ° C., and the maximum particle size is the same as in Example 1 of the present invention. It was obtained by classifying as follows.
  • PMMA polymethyl methacrylate
  • Example 3 was performed in order to investigate the correlation between the bead distribution and the scratch resistance of the organic-coated zinc-based plated steel sheet. Specifically, in a cross section having a length of 20 mm, the total number of beads is 10 or more, and beads satisfying the condition of ⁇ > 3t are 1.0%, 5.0% with respect to the total number of beads in the cross section.
  • the film was slightly damaged. Therefore, in a cross section having a length of 20 mm, the total number of beads is 10 or more, and the bead satisfying the condition of ⁇ > 3t is 1.0% or more with respect to the total number of beads in the cross section. It was found that the scratch resistance of the coated galvanized steel sheet was further improved.

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Abstract

La présente invention traite le problème de la fourniture d'une tôle en acier galvanisé recouverte d'un film organique qui, même lorsqu'elle est pressée avec une matrice qui présente des défauts sur la surface ou qui présente une surface rugueuse, est moins prompte à subir des dégâts sur le revêtement, tels que des défauts, de telle sorte que la fréquence d'inspection de maintenance de la matrice puisse être réduite ou que la matrice puisse être utilisée sans avoir besoin d'une maintenance dans le but de réduire le coût de production. Le problème est résolu avec une tôle en acier galvanisé recouverte d'un film organique (10) qui comprend une tôle en acier galvanisé (11) et un film de revêtement organique (15) qui contient des perles (14) et avec lequel la couche de revêtement à base de zinc (13) formée par placage sur au moins une surface de la base a été recouverte, ladite tôle étant caractérisée en ce que le film de revêtement organique (15) contient des perles (14) qui présentent un diamètre qui satisfait la relation ф > 3t où t est l'épaisseur du film (15) et ф est le diamètre des perles (14) et en ce que la résine qui constitue les perles, présente une température de transition vitreuse supérieure à 150 °C.
PCT/JP2014/050638 2013-01-17 2014-01-16 Tôle en acier galvanisé recouverte d'un film organique et procédé permettant de produire cette dernière WO2014112544A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2017002805A1 (fr) * 2015-07-02 2017-01-05 新日鐵住金株式会社 Tôle d'acier revêtue de noir
JP2017189908A (ja) * 2016-04-13 2017-10-19 新日鐵住金株式会社 プレコート金属板およびプレコート金属板の製造方法
JP6402846B1 (ja) * 2017-03-10 2018-10-10 新日鐵住金株式会社 有機樹脂被覆めっき鋼板
JP2019505608A (ja) * 2015-12-09 2019-02-28 ポスコＰｏｓｃｏ 樹脂組成物およびこれを用いた黒色樹脂鋼板、およびその製造方法
WO2024071189A1 (fr) * 2022-09-27 2024-04-04 日本製鉄株式会社 Tôle d'acier traitée en surface

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JP2007283718A (ja) * 2006-04-19 2007-11-01 Nippon Steel & Sumikin Coated Sheet Corp 塗装金属板
JP2011230425A (ja) * 2010-04-28 2011-11-17 Jfe Steel Corp 塗装鋼板、加工品および薄型テレビ用パネル

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JPH09111183A (ja) * 1995-10-20 1997-04-28 Kansai Paint Co Ltd 塗料組成物及びワンコート塗装鋼板
JP2007269010A (ja) * 2006-03-08 2007-10-18 Jfe Steel Kk 塗装鋼板、加工品および薄型テレビ用パネルならびに塗装鋼板の製造方法
JP2007283718A (ja) * 2006-04-19 2007-11-01 Nippon Steel & Sumikin Coated Sheet Corp 塗装金属板
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017002805A1 (fr) * 2015-07-02 2017-01-05 新日鐵住金株式会社 Tôle d'acier revêtue de noir
JP6132078B1 (ja) * 2015-07-02 2017-05-24 新日鐵住金株式会社 黒色塗装鋼板
CN107429407A (zh) * 2015-07-02 2017-12-01 新日铁住金株式会社 黑色涂装钢板
JP2019505608A (ja) * 2015-12-09 2019-02-28 ポスコＰｏｓｃｏ 樹脂組成物およびこれを用いた黒色樹脂鋼板、およびその製造方法
US11066573B2 (en) 2015-12-09 2021-07-20 Posco Resin composition, black resin coated steel sheet using same, and method of preparing same
JP2017189908A (ja) * 2016-04-13 2017-10-19 新日鐵住金株式会社 プレコート金属板およびプレコート金属板の製造方法
JP6402846B1 (ja) * 2017-03-10 2018-10-10 新日鐵住金株式会社 有機樹脂被覆めっき鋼板
US11377744B2 (en) 2017-03-10 2022-07-05 Nippon Steel Corporation Organic resin-coated plated steel sheet
WO2024071189A1 (fr) * 2022-09-27 2024-04-04 日本製鉄株式会社 Tôle d'acier traitée en surface

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