WO2023132106A1 - 潤滑皮膜被覆亜鉛系めっき鋼板およびその製造方法 - Google Patents
潤滑皮膜被覆亜鉛系めっき鋼板およびその製造方法 Download PDFInfo
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- WO2023132106A1 WO2023132106A1 PCT/JP2022/035046 JP2022035046W WO2023132106A1 WO 2023132106 A1 WO2023132106 A1 WO 2023132106A1 JP 2022035046 W JP2022035046 W JP 2022035046W WO 2023132106 A1 WO2023132106 A1 WO 2023132106A1
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- WIPO (PCT)
- Prior art keywords
- steel sheet
- zinc
- plated steel
- film
- lubricating film
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 106
- 239000010959 steel Substances 0.000 title claims abstract description 106
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 106
- 239000011701 zinc Substances 0.000 claims abstract description 106
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 6
- 229920001225 polyester resin Polymers 0.000 claims abstract description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004645 polyester resin Substances 0.000 claims abstract description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 50
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 29
- 239000008397 galvanized steel Substances 0.000 claims description 29
- 239000003973 paint Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 abstract description 6
- 239000004925 Acrylic resin Substances 0.000 abstract description 6
- 235000019592 roughness Nutrition 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 58
- 239000010410 layer Substances 0.000 description 39
- 238000007747 plating Methods 0.000 description 14
- 238000005238 degreasing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010960 cold rolled steel Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- -1 zinc-aluminum-magnesium Chemical compound 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007591 painting process Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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 lubricating film-coated galvanized steel sheet with excellent slidability in press forming and a method for producing the same.
- the present invention relates to a lubricating film-coated galvanized steel sheet having a lubricating film that is excellent in formability even during severe drawing, and a method for producing the same.
- Galvanized steel sheets are widely used in a wide range of fields, mainly for automobile bodies.
- a galvanized steel sheet is usually used after being press-formed.
- zinc-based plated steel sheets have the disadvantage of being inferior to cold-rolled steel sheets in terms of press formability. This is because the sliding resistance of the galvanized steel sheet in the press die is greater than that of the cold-rolled steel sheet. That is, the zinc-based plated steel sheet having high sliding resistance is difficult to flow into the press die at the portion where the sliding resistance between the die and the bead is high, and the steel sheet is likely to break.
- a method of applying high-viscosity lubricating oil is widely used as a method of improving press formability when using zinc-based plated steel sheets.
- the lubricating oil is highly viscous, coating defects occur due to insufficient degreasing in the coating process.
- problems such as unstable press performance due to lack of oil during pressing. For this reason, it is required to improve the press formability of the galvanized steel sheet itself.
- Patent Document 1 describes a metal plate coated with a lubricating film in which a solid lubricant protrudes from the resin film surface by 0.01 to 1.5 ⁇ m.
- Patent Document 2 describes a lubricating surface-treated metal product with excellent press-moldability, which is coated with a coating of 0.5 to 5 ⁇ m containing a lubricant in polyurethane resin.
- Patent Document 3 describes a technique for forming an alkali-soluble organic film on a steel plate by adding a lubricant to an epoxy resin.
- Patent Documents 1 to 3 although lubricity is exhibited by the lubricating effect of the contained lubricant, etc., the press formability was not necessarily sufficient in complicated forming. In particular, when the surface roughness of the steel sheet changed, it was not possible to stably obtain good press formability.
- the present invention has been made in view of such circumstances, and in a zinc-based plated steel sheet that is subjected to complicated forming that is difficult to press-form, the sliding resistance at the risk of cracking during press-forming is small, and the surface Lubricating film-coated zinc with lubricating film that has excellent press formability in areas where die galling is expected to occur due to high pressure, especially for steel sheets with a wide range of surface roughness.
- An object of the present invention is to provide a system plated steel sheet and a method for manufacturing the same.
- a zinc-based plated steel sheet is a steel sheet on which a zinc-based plating film is formed.
- Zinc-based plating films do not intentionally add components other than zinc, and zinc plating consists of zinc and unavoidable impurities. Examples include zinc plating to which compounds such as alumina and silica are added.
- the present inventors have made intensive studies to solve the above problems. As a result, in order to dramatically improve the press formability, it is necessary to add a metallic zinc layer with a coating amount of 5 g/m 2 or more on the surface of the steel sheet to the upper layer of the zinc-based plated steel sheet, which has a melting point of 120°C or more and 140°C or less and an average
- the present inventors have found that the above problems can be solved by forming an organic resin film containing polyolefin wax having a particle size of 3.0 ⁇ m or less and controlling the surface roughness of the steel sheet and the amount of film adhered.
- a lubricating-film-coated zinc-based plated steel sheet having, on at least one side thereof, a metallic zinc layer having a coating amount of 5 g/m 2 or more as a lower layer and a lubricating film containing an organic resin and wax as an upper layer, wherein the organic
- the resin is at least one of acrylic resin, epoxy resin, urethane resin, phenol resin, vinyl acetate resin, and polyester resin, and the wax has a melting point of 120° C. or higher and 140° C. or lower, and an average particle size.
- lubricating film-coated zinc-based plated steel sheet having a relationship with Ra ( ⁇ m) within the range of the following formula (1).
- W ⁇ 0.12 ⁇ Ra 2 +0.1 (1) [2] Described in [1], wherein the relationship between the coating amount W (g/m 2 ) per side of the coating and the arithmetic mean roughness Ra ( ⁇ m) of the metallic zinc layer surface is within the range of the following formula (2) lubricating film-coated galvanized steel sheet.
- [6] The lubricating film-coated zinc-plated steel sheet according to any one of [1] to [5], wherein the wax content in the film is less than 50% by mass.
- [7] The lubricating film-coated zinc-plated steel sheet according to any one of [3] to [6], wherein the amount W of the coating per one side is 0.9 g/m 2 or less.
- [8] The lubricating film-coated zinc-plated steel sheet according to any one of [1] to [7], wherein the organic resin is an alkali-soluble resin.
- a method for producing a lubricating film-coated galvanized steel sheet comprising applying a paint to at least one side of a galvanized steel sheet and drying the paint.
- the metal zinc layer is a plating layer formed on a steel plate such as cold-rolled steel plate or hot-rolled steel plate.
- a zinc-based plated steel sheet is a steel sheet such as a cold-rolled steel sheet or a hot-rolled steel sheet on which a metallic zinc layer is formed.
- the present invention it is possible to obtain a galvanized steel sheet with excellent press formability by significantly reducing the coefficient of friction between a lubricating film-coated galvanized steel sheet and a mold or the like. Therefore, when the present invention is applied to a zinc-based plated steel sheet with relatively low strength that is subjected to complicated forming, it will have excellent press formability stably.
- high strength assumes a tensile strength (TS) of 440 MPa or more, and relatively low strength assumes a TS of less than 440 MPa.
- TS tensile strength
- FIG. 1 is a schematic front view showing a friction coefficient measuring device.
- FIG. 2 is a schematic perspective view showing the bead shape and dimensions in FIG.
- FIG. 3 is a graph showing the surface roughness of various lubricating film-coated zinc-based plated steel sheets and the coefficient of friction at various film thicknesses for paints that are the subject of the present invention.
- FIG. 4 is a diagram showing the surface roughness of various lubricating film-coated zinc-based plated steel sheets and the coefficient of friction at various film thicknesses for paints not covered by the present invention.
- the present invention provides a lubricating-coated zinc-based steel sheet having, on at least one side thereof, a metal zinc layer having a coating amount of 5 g/m 2 or more as a lower layer and a coating containing an organic resin and wax as an upper layer, wherein the wax is is a polyolefin wax having a melting point of 120° C. or more and 140° C. or less and an average particle size of 3.0 ⁇ m or less, and the wax content in the film is 10% by mass or more.
- the relationship between the amount W (g/m 2 ) deposited per one side of the film and the arithmetic mean roughness Ra ( ⁇ m) of the surface of the metallic zinc layer is in the range of the following formula (1). W ⁇ 0.12 ⁇ Ra 2 +0.1 (1)
- the method for producing the metallic zinc layer in the present invention is not particularly limited, and for example, it may be formed by applying zinc-based plating on a steel sheet by various manufacturing methods such as hot dip plating, electroplating, vapor deposition plating, and thermal spraying. can be done. Also, an alloyed hot-dip galvanized steel sheet that is subjected to alloying treatment after galvanizing treatment can be used. Furthermore, even if a zinc-based plated steel sheet containing a metal other than zinc, such as zinc-aluminum alloy plating, zinc-aluminum-magnesium alloy plating, or zinc-nickel alloy plating, is used as the metallic zinc layer, the adhesion amount of metallic zinc is It may be 5 g/m 2 or more.
- the presence of the metallic zinc layer as the lower layer of the organic lubricating film promotes adhesion between the mold and the wax component in the organic lubricating film during sliding, making it easier for the mold to be coated with the wax component.
- a superior lubricating effect can be obtained compared to the case without
- the metal zinc layer is softer than the steel plate, the deformation resistance during sliding is small, and the coefficient of friction tends to be low. If the metal zinc layer is less than 5 g/m 2 , the lubricating effect of the zinc layer described above may not be sufficiently obtained, and the corrosion resistance is poor.
- the wax used in the present invention may be a polyolefin wax having a melting point of 120°C or higher and 140°C or lower and an average particle size of 3.0 ⁇ m or lower, and other characteristics are not particularly limited.
- polyolefin wax is used as wax is that it has low surface energy and self-lubricating properties, so good lubricity can be obtained.
- it is relatively easy to adjust the melting point of polyolefin to 120° C. or higher and 140° C. or lower by controlling the density and molecular weight.
- the lubricating film component mixed with the organic resin is formed into a semi-molten state by sliding during press molding. It is possible to coat the surface, and an excellent lubrication effect can be obtained by suppressing direct contact between the mold and the steel plate. If the melting point is less than 120° C., the wax is completely melted by frictional heat caused by sliding during press molding, and the wax itself cannot provide sufficient lubricating effect. On the other hand, if the melting point exceeds 140° C., it will not melt during sliding, and a sufficient lubricating effect cannot be obtained, and a mold coating effect cannot be obtained.
- the wax in the film efficiently adheres to the mold during sliding during press molding, causing a phenomenon that makes it difficult for the film to fall off, resulting in a high lubricating effect. It is considered possible. If the melting point is less than 120° C., even if the film adheres to the mold, the adhesion is weak and the film tends to come off when slid. If the melting point is above 140°C, the coating will be difficult to adhere to the mold. Furthermore, it is preferable that the melting point is 125° C. or higher and 135° C. or lower.
- the melting point of wax is the melting temperature measured based on JIS K 7121:1987 "Method for measuring transition temperature of plastics”.
- the average particle size of the wax is preferably 1.5 ⁇ m or less.
- the average particle size of the wax is more preferably 0.5 ⁇ m or less, still more preferably 0.3 ⁇ m or less.
- the average particle size of the wax is preferably 0.01 ⁇ m or more. If it is less than 0.01 ⁇ m, it tends to dissolve in lubricating oil during sliding, and sufficient lubricity improvement effect may not be exhibited.
- the average particle size of the wax is more preferably 0.03 ⁇ m or more.
- the average particle diameter is the median diameter of the volume average diameter, and is determined by a laser diffraction/scattering method. For example, it can be determined by measuring a sample diluted with pure water using a laser diffraction/scattering particle size distribution analyzer partica (registered trademark) LA-960V2 (manufactured by HORIBA, Ltd.).
- polyethylene waxes it is preferable to use polyethylene wax because the highest lubricating effect is obtained when polyethylene wax is used.
- the mass ratio of wax in the film is set to 10% by mass or more. If it is less than 10% by mass, a sufficient lubricating effect cannot be obtained. A particularly good lubricating effect can be obtained if the mass ratio of the wax in the coating is 15 mass % or more.
- the mass ratio of the wax in the film is preferably less than 50% by mass. If it is 50% by mass or more, the wax tends to fall off due to the lack of the base resin component, the adhesion to the zinc-based plated steel sheet is poor, and the film may not exist stably.
- sufficient degreasing may not be obtained in the alkaline degreasing process in the painting process. In some cases, the coating is not sufficiently removed and the film remains, degrading the paintability.
- the mass ratio of wax in the film is more preferably 30 mass % or less.
- the mass ratio of the wax in the film is the mass ratio of the solid content of the wax in the film to the total mass of the mass of the solid content of the resin in the film and the mass of the solid content of the wax in the film.
- the organic resin plays a role as a binder that holds the wax on the surface of the zinc-based plated steel sheet.
- the above-described sliding effect of the mold coating of the mixture of wax and organic resin formed during sliding cannot be exhibited with the inorganic binder because of its low affinity with the polyolefin wax.
- At least one of acrylic resin, epoxy resin, urethane resin, phenol resin, vinyl acetate resin, and polyester resin can be used as the organic resin.
- the acrylic resin used in the present invention is one selected from unsaturated monocarboxylic acids having one carboxyl group in the molecule such as acrylic acid and methacrylic acid, esters of the above unsaturated monocarboxylic acids, and styrene. Alternatively, it is a polymer or copolymer consisting of a plurality of them, or derivatives such as sodium salts, potassium salts, ammonium salts, and amine salts thereof.
- Acrylic resin having a fatty acid having two or more carboxyl groups in the molecule as a monomer
- the paint stability may be poor.
- Acrylic resin is used as a monomer.
- epoxy resin is not particularly limited, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin and the like can be mentioned.
- the urethane-based resin is not particularly limited, it preferably has a carboxy group in the molecule.
- the phenolic resin is not particularly limited, but a resol-based phenolic resin that can be dissolved or dispersed in an aqueous solvent is preferable.
- polyester-based resin is not particularly limited, a polyester resin containing a monomer having a carboxy group as a constituent component is preferred.
- these resins can be used in combination of two or more. Furthermore, by using an alkali-soluble organic resin, it becomes possible to remove the film by alkaline degreasing in the painting process, and the subsequent paintability is improved.
- surface conditioners may be included as components other than the organic resin and wax.
- a rust preventive agent for improving rust resistance can be added.
- a film with a wide range of adhesion amount is formed on a zinc-based plated steel sheet with a wide range of surface roughness to evaluate press formability. It was found that stable and good press formability is satisfied only in the region that satisfies the relational expression between the surface roughness of the zinc-based plated steel sheet and the coating amount. In general, the higher the surface roughness of a galvanized steel sheet, the thinner the lubricating film on the convex portions of the steel sheet. It becomes easy to be exposed, and it becomes difficult to obtain a lubricating effect.
- the following is the coating amount range that shows good press formability.
- the relationship between the coating amount W (g/m 2 ) per side of the coating and the arithmetic mean roughness Ra ( ⁇ m) of the metallic zinc layer surface satisfies the formula (1): W ⁇ 0.12 ⁇ Ra 2 +0.1 Good press formability can be obtained within the range. In the case of W ⁇ 0.12 ⁇ Ra 2 +0.1, the coating amount is insufficient, the effect of protecting the mold side is not sufficiently obtained, and good press moldability cannot be obtained.
- the ones that mainly contribute to the slidability are the components of the coating present on the convex portions of the zinc-based plated steel sheet that come into contact with the die during press working. It is considered that the area of the steel plate convex portion in contact with the mold tends to decrease in proportion to Ra2 . Therefore, it is considered that by increasing the coating amount in proportion to Ra2 , it is possible to secure a sufficient amount of the coating component that contributes to the slidability.
- the coating amount W per one side of the film is 2.0 g/m 2 or less. If it exceeds 2.0 g/m 2 , film removal properties and weldability may deteriorate. It is particularly preferable that the adhesion amount W is 0.9 g/m 2 or less. If the adhesion amount W is 0.9 g/m 2 or less, the film removal properties are particularly good.
- the coating amount can be determined by dividing the difference in weight of the zinc-based steel sheet before and after coating by the area, or by completely removing the coating on the zinc-based steel sheet after coating with an alkaline aqueous solution or organic solvent. It can be obtained by dividing the weight difference of the galvanized steel sheet by the area.
- the arithmetic mean roughness Ra of the metal zinc layer surface is preferably 0.4 ⁇ m or more and 2.5 ⁇ m or less.
- the arithmetic mean roughness Ra of the surface of the metal zinc layer is less than 0.4 ⁇ m, fine scratches that may occur during press molding may be easily noticeable, and galling may occur during press molding.
- Ra exceeds 2.5 ⁇ m, the required coating amount increases, which may increase the production cost and deteriorate the sharpness after coating.
- the arithmetic mean roughness Ra ( ⁇ m) of the metal zinc layer surface can be measured according to JIS B 0633:2001 (ISO 4288:1996). For example, when Ra is greater than 0.1 and less than or equal to 2, the cutoff value and the reference length are set to 0.8 mm, and the evaluation length is set to 4 mm. When Ra exceeds 2 and is 10 or less, the cut-off value and the reference length are set to 2.5 mm, and the evaluation length is set to 12.5 mm.
- an organic resin film containing polyolefin wax having a melting point of 120° C. or higher and 140° C. or lower and an average particle size of 3.0 ⁇ m or less on the upper layer of the metallic zinc layer of a zinc-based plated steel sheet an organic resin is dissolved or dispersed in a solvent.
- a method of coating the surface of the steel sheet with a paint obtained by adding wax to an organic resin solution or emulsion and drying it can be applied.
- the mass ratio of the coating components (organic resin and polyolefin wax) in the paint is preferably 1% by mass or more and 25% by mass or less.
- the coating method is not particularly limited, but examples thereof include a method using a roll coater or a bar coater, and a coating method using spraying, dipping, or brushing.
- a general method can be used to dry the zinc-based plated steel sheet after application. For example, drying with hot air, drying with an IH heater, and infrared heating can be used.
- the maximum temperature reached by the zinc-based plated steel sheet during drying is preferably 60°C or higher and 140°C or lower. If the drying temperature is less than 60°C, it may take a long time to dry and the rust resistance may be poor. If the temperature exceeds 140° C., the wax melts and coalesces, and the particle size becomes coarse, which may deteriorate the lubricity.
- the relationship between the coating amount W (g/m 2 ) per side of the coating and the arithmetic mean roughness Ra ( ⁇ m) of the surface of the metallic zinc layer is expressed by the formula (1): If W ⁇ 0.12 ⁇ Ra 2 +0.1 is finally satisfied, a lubricating film-coated zinc-based plated steel sheet having good press formability can be produced.
- the amount W (g/m 2 ) or the arithmetic mean roughness of the surface of the metallic zinc layer is adjusted so as to satisfy the formula (1).
- a step of intentionally changing at least one of Ra ( ⁇ m) may be further provided.
- the adhesion per side of the coating is adjusted so as to satisfy the above formula (1) according to the target value or measured value of the arithmetic mean roughness Ra ( ⁇ m) of the surface of the metal zinc layer It includes a step of determining the amount W (g/m 2 ), and adjusting the coating amount so as to achieve the determined adhesion amount W in the coating step. More specifically, the value of the arithmetic mean roughness Ra ( ⁇ m) of the surface of the metal zinc layer is substituted into the above formula (1), and the surface of the coating is adjusted so as to satisfy the substituted formula (1). to determine the adhesion amount W (g/m 2 ).
- the surface roughness of the metallic zinc layer of the lubricating film-coated zinc-based plated steel sheet may be measured before the lubricating film is applied, or after the lubricating film is completely removed with an alkaline aqueous solution or an organic solvent. good too.
- the surface roughness of the steel sheet after removing the scale by pickling can be adjusted by adjusting the thickness of the scale during hot rolling according to the amount of Si added to the steel sheet. .
- the surface roughness of the steel sheet can also be adjusted by adjusting the intensity of descaling (a process of pulverizing and removing scale with water pressure) during hot rolling.
- the surface roughness of the steel sheet can be adjusted by changing the roll load or roll surface roughness during temper rolling.
- the surface roughness of the zinc-based coating layer can be adjusted by changing the roll load or roll surface roughness during temper rolling of the steel sheet after zinc-based plating.
- Ra ( ⁇ m) and any one of Ra ( ⁇ m) may be implemented as a method for determining manufacturing conditions for a galvanized steel sheet. Such a method for determining manufacturing conditions may be performed as a part of steps in the method for manufacturing a lubricating film-coated zinc-based plated steel sheet, or may be performed as a single step.
- Fig. 1 is a schematic front view showing a friction coefficient measuring device.
- a friction coefficient measurement sample 1 taken from a test material is fixed to a sample table 2, and the sample table 2 is fixed to the upper surface of a horizontally movable slide table 3.
- a vertically movable slide table support 5 having a roller 4 in contact with the slide table 3 is provided on the lower surface of the slide table 3.
- a first load cell 7 for measuring is attached to the slide table support base 5 .
- a second load cell 8 is attached to one end of the slide table 3 for measuring the sliding resistance force F for moving the slide table 3 in the horizontal direction while the pressing force is applied.
- the surface of the sample 1 was coated with press cleaning oil Pleton (registered trademark) R352L manufactured by Sugimura Chemical Industry Co., Ltd. for the test.
- Fig. 2 is a schematic perspective view showing the shape and dimensions of the beads used.
- the lower surface of the bead 6 slides against the surface of the sample 1 .
- the shape of the bead 6 shown in FIG. 2 has a width of 10 mm, a length of 59 mm in the sliding direction of the sample, and lower surfaces at both ends of the sliding direction having a curvature of 4.5 mmR. It has a plane with a directional length of 50 mm.
- the friction coefficient measurement test was performed using the bead shown in FIG. 2 with a pressing load N of 400 kgf and a sample withdrawal speed (horizontal movement speed of the slide table 3) of 20 cm/min.
- each test piece was degreased with an alkaline degreasing agent, Fine Cleaner (registered trademark) E6403 (manufactured by Nihon Parkerizing Co., Ltd.). This treatment consisted of immersing the test piece in a degreasing liquid having a degreasing agent concentration of 20 g/L and a temperature of 40° C. for a predetermined period of time, followed by washing with tap water.
- Fine Cleaner registered trademark
- E6403 manufactured by Nihon Parkerizing Co., Ltd.
- the surface carbon strength of the test piece after such treatment was measured using a fluorescent X-ray analyzer, and the measured value was combined with the previously measured surface carbon strength before degreasing and the measured surface carbon strength of the untreated steel plate. was used to calculate the film peeling rate according to the following formula.
- Film peeling rate (%) [(carbon strength before degreasing - carbon strength after degreasing) / (carbon strength before degreasing - carbon strength of untreated steel sheet)] x 100
- the film removal property of the lubricating film-coated zinc-based plated steel sheet was evaluated according to the following criteria based on the immersion time in an alkaline degreasing solution at which the film peeling rate was 98% or more.
- the film removal property was judged to be good in the following cases of ⁇ and ⁇ . ⁇ (particularly good): within 30 seconds ⁇ (good): over 30 seconds and within 60 seconds ⁇ (insufficient): over 60 seconds and within 120 seconds ⁇ (bad): over 120 seconds
- Tables 3 and 4 The results obtained are shown in Tables 3 and 4.
- the determination of formula (1) and the determination of formula (2) were performed by ⁇ when the formulas (1) and (2) were satisfied, and by x when the formulas (2) were not satisfied.
- the lubricating film-coated galvanized steel sheets of the invention examples all have excellent press formability.
- the galvanized steel sheets of Comparative Examples which do not have the technical features of the present invention, are all inferior in press formability.
- the adhesion amount W (g/m 2 ) of the lubricating film per one side is W ⁇ 0.25 ⁇ Ra 2 +0.1, and the lubricating film
- the melting point of the wax is 125° C. or higher and 135° C. or lower, and the average grain size of the wax in the lubricating film is 0.01 ⁇ m or higher and 0.5 ⁇ m or lower, and the lubricating film-coated galvanized steel sheet has particularly good press formability. is clear.
- the galvanized steel sheet coated with a paint that is not the subject of the present invention tended to exhibit a higher coefficient of friction as the surface roughness of the galvanized steel sheet increased.
- the lubricating film-coated zinc-based steel sheet that is coated with the paint that is the subject of the present invention and that satisfies the formula (1) can be obtained even if the surface roughness of the zinc-based steel sheet changes. Since it stably exhibits a low coefficient of friction, good press formability is stably obtained even when the surface roughness of the galvanized steel sheet changes during production.
- the film removal property of the lubricating film-coated zinc-based plated steel sheet of the example of the present invention is such that the mass ratio of wax in the film is 50% or more and/or the adhesion amount W per one side of the lubricating film is more than 0.9 g/m 2 . It was evaluated as ⁇ (particularly good) except for some cases.
- the lubricating film-coated galvanized steel sheet of the present invention has excellent press formability, so it can be applied in a wide range of fields, mainly for automobile bodies.
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- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
[1]少なくとも片面に、下層として付着量5g/m2以上の金属亜鉛層、及び、上層として有機樹脂およびワックスを含む潤滑皮膜が形成された潤滑皮膜被覆亜鉛系めっき鋼板であって、前記有機樹脂がアクリル系樹脂、エポキシ系樹脂、ウレタン系樹脂、フェノール系樹脂、酢酸ビニル系樹脂、ポリエステル系樹脂の少なくとも1種以上であり、前記ワックスは融点が120℃以上140℃以下、かつ平均粒径が3.0μm以下のポリオレフィンワックスであり、皮膜中のワックスの割合が10質量%以上であり、前記皮膜の片面当たりの付着量W(g/m2)と金属亜鉛層表面の算術平均粗さRa(μm)との関係が下記式(1)の範囲である潤滑皮膜被覆亜鉛系めっき鋼板。
W≧0.12×Ra2+0.1・・・(1)
[2]前記皮膜の片面当たりの付着量W(g/m2)と金属亜鉛層表面の算術平均粗さRa(μm)との関係が下記式(2)の範囲である[1]に記載の潤滑皮膜被覆亜鉛系めっき鋼板。
W≧0.25×Ra2+0.1・・・(2)
[3]前記皮膜の片面当たりの付着量Wが2.0g/m2以下である[1]または[2]に記載の潤滑皮膜被覆亜鉛系めっき鋼板。
[4]前記金属亜鉛層表面の算術平均粗さRaが0.4μm以上2.5μm以下である[1]~[3]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
[5]前記ワックスの平均粒径が0.01μm以上0.5μm以下である[1]~[4]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
[6]前記皮膜中のワックスの割合が50質量%未満である[1]~[5]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
[7]前記皮膜の片面当たりの付着量Wが0.9g/m2以下である[3]~[6]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
[8]前記有機樹脂がアルカリ可溶性樹脂である[1]~[7]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
[9][1]~[8]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法であって、[1]~[8]のいずれかに記載の有機樹脂およびワックスが含まれる塗料を、亜鉛系めっき鋼板の少なくとも片面に塗布し乾燥する潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
[10]前記乾燥時の鋼板の最高到達温度が60℃以上140℃以下である[9]に記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
[11]前記塗料における前記有機樹脂およびワックスの割合が1質量%以上25質量%以下である[9]または[10]に記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
[12] 前記式(1)を満足しないときに、前記式(1)を満足するように前記付着量W(g/m2)又は前記金属亜鉛層表面の算術平均粗さRa(μm)のうち少なくとも一つを変更する工程をさらに備える[9]~[11]のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
W≧0.12×Ra2+0.1・・・(1)
プレス成形性を評価するために、各供試材の摩擦係数を以下のようにして測定した。
本発明に係る潤滑皮膜被覆亜鉛系めっき鋼板が、自動車用途で使用される場合を想定して、脱脂時の脱膜性を評価した。鋼板の脱膜性を求めるために、まず、各試験片をアルカリ脱脂剤のファインクリーナー(登録商標)E6403(日本パーカライジング(株)製)で脱脂処理した。かかる処理は、試験片を、脱脂剤濃度20g/L、温度40℃の脱脂液に所定の時間浸漬し、水道水で洗浄することとした。かかる処理後の試験片に対し、蛍光X線分析装置を用いて表面炭素強度を測定し、かかる測定値と予め測定しておいた脱脂前表面炭素強度および無処理鋼板の表面炭素強度の測定値を用いて、以下の式により皮膜剥離率を算出した。
潤滑皮膜被覆亜鉛系めっき鋼板の脱膜性は、かかる皮膜剥離率が98%以上となるアルカリ脱脂液への浸漬時間により、以下に示す基準で評価した。下記◎と〇の場合に脱膜性が良好であると判定した。
◎(特に良好):30秒以内
○(良好) :30秒超え60秒以内
△(不十分) :60秒超え120秒以内
×(不良) :120秒超え
2 試料台
3 スライドテーブル
4 ローラ
5 スライドテーブル支持台
6 ビード
7 第1ロードセル
8 第2ロードセル
9 レール
Claims (12)
- 少なくとも片面に、下層として付着量5g/m2以上の金属亜鉛層、及び、上層として有機樹脂およびワックスを含む皮膜が形成された潤滑皮膜被覆亜鉛系めっき鋼板であって、前記有機樹脂がアクリル系樹脂、エポキシ系樹脂、ウレタン系樹脂、フェノール系樹脂、酢酸ビニル系樹脂、ポリエステル系樹脂の少なくとも1種以上であり、前記ワックスは融点が120℃以上140℃以下、かつ平均粒径が3.0μm以下のポリオレフィンワックスであり、皮膜中のワックスの割合が10質量%以上であり、前記皮膜の片面当たりの付着量W(g/m2)と金属亜鉛層表面の算術平均粗さRa(μm)との関係が下記式(1)の範囲である潤滑皮膜被覆亜鉛系めっき鋼板。
W≧0.12×Ra2+0.1・・・(1) - 前記皮膜の片面当たりの付着量W(g/m2)と金属亜鉛層表面の算術平均粗さRa(μm)との関係が下記式(2)の範囲である請求項1に記載の潤滑皮膜被覆亜鉛系めっき鋼板。
W≧0.25×Ra2+0.1・・・(2) - 前記皮膜の片面当たりの付着量Wが2.0g/m2以下である請求項1または2に記載の潤滑皮膜被覆亜鉛系めっき鋼板。
- 前記金属亜鉛層表面の算術平均粗さRaが0.4μm以上2.5μm以下である請求項1~3のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
- 前記ワックスの平均粒径が0.01μm以上0.5μm以下である請求項1~4のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
- 前記皮膜中のワックスの割合が50質量%未満である請求項1~5のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
- 前記皮膜の片面当たりの付着量Wが0.9g/m2以下である請求項3~6のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
- 前記有機樹脂がアルカリ可溶性樹脂である請求項1~7のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板。
- 請求項1~8のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法であって、請求項1~8のいずれかに記載の有機樹脂およびワックスが含まれる塗料を、亜鉛系めっき鋼板の少なくとも片面に塗布し乾燥する潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
- 前記乾燥時の鋼板の最高到達温度が60℃以上140℃以下である請求項9に記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
- 前記塗料における前記有機樹脂およびワックスの割合が1質量%以上25質量%以下である請求項9または10に記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
- 前記式(1)を満足しないときに、前記式(1)を満足するように前記付着量W(g/m2)又は前記金属亜鉛層表面の算術平均粗さRa(μm)のうち少なくとも一つを変更する工程をさらに備える請求項9~11のいずれかに記載の潤滑皮膜被覆亜鉛系めっき鋼板の製造方法。
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JP2006022363A (ja) * | 2004-07-07 | 2006-01-26 | Nippon Steel Corp | 加工部耐食性に優れた表面処理鋼板 |
JP2010121198A (ja) * | 2008-11-21 | 2010-06-03 | Jfe Steel Corp | 表面処理鋼板および電子機器筐体 |
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JPS53113108U (ja) * | 1977-02-15 | 1978-09-08 | ||
JP3061157U (ja) * | 1999-01-30 | 1999-09-17 | 孝雄 岡 | 上体凭れ具 |
JP3187631U (ja) * | 2013-09-26 | 2013-12-05 | 知司 小林 | 座椅子 |
JP2017042451A (ja) * | 2015-08-27 | 2017-03-02 | 株式会社宮武製作所 | 椅子になる座椅子 |
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JPH1052881A (ja) | 1996-08-09 | 1998-02-24 | Kobe Steel Ltd | 耐型かじり性および耐食性に優れた樹脂被覆金属板およびその製造方法 |
JP2000167981A (ja) | 1998-12-04 | 2000-06-20 | Nkk Corp | 接着性、耐型カジリ性に優れたアルカリ可溶型有機皮膜被覆鋼板 |
JP2000309747A (ja) | 1999-02-26 | 2000-11-07 | Nippon Steel Corp | プレス成形性、耐かじり性に優れたアルカリ可溶型潤滑皮膜を形成可能な塗料組成物およびこの組成物を使用した潤滑表面処理金属製品 |
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JP2010121198A (ja) * | 2008-11-21 | 2010-06-03 | Jfe Steel Corp | 表面処理鋼板および電子機器筐体 |
WO2012133671A1 (ja) * | 2011-03-29 | 2012-10-04 | 新日本製鐵株式会社 | 表面処理鋼板及びその製造方法 |
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