WO2011065514A1 - 亜鉛系めっき鋼板 - Google Patents
亜鉛系めっき鋼板 Download PDFInfo
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- WO2011065514A1 WO2011065514A1 PCT/JP2010/071190 JP2010071190W WO2011065514A1 WO 2011065514 A1 WO2011065514 A1 WO 2011065514A1 JP 2010071190 W JP2010071190 W JP 2010071190W WO 2011065514 A1 WO2011065514 A1 WO 2011065514A1
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- WIPO (PCT)
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- steel sheet
- organic
- resin
- galvanized steel
- crystalline layered
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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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
- 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
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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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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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
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
Definitions
- the present invention relates to a galvanized steel sheet having small press resistance and excellent press formability during press forming.
- Zinc-based galvanized steel sheets are widely used in a wide range of fields centering on automobile body applications. In such applications, they are used after being press-formed.
- galvanized steel sheets have the disadvantage that they are inferior in press formability compared to cold rolled steel sheets. This is because the sliding resistance of the surface-treated steel sheet in the press die is larger than that of the cold-rolled steel sheet.
- Patent Document 1 and Patent Document 2 disclose an oxide film mainly composed of zinc by subjecting the surface of a galvanized steel sheet to electrolytic treatment, immersion treatment, coating oxidation treatment, or heat treatment. Discloses a technique for improving weldability and workability by forming a slab.
- Patent Document 3 discloses that P-oxidation is applied to the surface of a zinc-based plated steel sheet by immersing the plated steel sheet in an aqueous solution containing 5 to 60 g / l of sodium phosphate, pH 2-6, or performing electrolytic treatment, or applying the aqueous solution.
- a technique for improving press moldability and chemical conversion property by forming an oxide film mainly composed of an object is disclosed.
- Patent Document 4 discloses a technique for improving press formability and chemical conversion treatment by generating Ni oxide on the surface of a galvanized steel sheet by electrolytic treatment, immersion treatment, coating oxidation treatment, or heat treatment. Yes.
- JP-A-53-60332 Japanese Patent Laid-Open No. 2-190483 JP-A-4-88196 Japanese Patent Laid-Open No. 3-191093
- An object of the present invention is to improve the above-mentioned problems and to provide a zinc-based plated steel sheet having excellent press formability even in difficult-to-form materials such as a high-strength galvanized steel sheet that increases the surface pressure during press forming. To do.
- the frictional resistance is reduced by suppressing the contact between the galvanized layer and the mold.
- the amount of wear of the film increases, so that a sufficient effect cannot be obtained if the sliding distance exceeds a certain amount. Therefore, the present inventors have intensively studied to solve the above problems. As a result, it has been found that to dramatically improve the slidability, it is effective to form a film in which the crystalline layered material is coated on the surface of the galvanized steel sheet.
- the present invention has been made based on the above findings, and the gist thereof is as follows.
- a zinc-based plated steel sheet comprising 0.5 part by weight or more of a crystalline layered material as a solid content with respect to parts.
- the crystalline layered material is a layered double hydroxide represented by [M 2+ 1-X M 3+ X (OH) 2] [A n-] x / n ⁇ zH 2 O
- the M 2+ is one or more of Mg 2+ , Ca 2+ , Fe 2+ , Ni 2+ , Zn 2+ , Pb 2+ , Sn 2+
- the M 3+ is Al 3+ , Fe 3+ , Cr 3+ , 3 / 4Zr 4+, is one or more of Mo 3+, wherein a n- is OH -, F -, CO 3 2-, Cl -, Br -, (C 2 O 4) 2-, I -, (NO 3 ) ⁇ , (SO 4 ) 2 ⁇ , (BrO 3 ) ⁇ , (IO 3 ) ⁇ , (V 10 O 28 ) 6 ⁇ , (Si 2 O 5 ) 2 ⁇ , (ClO 4
- the crystalline layered product is [M 2+ 1-X M 3+ X (OH) 2] layered double hydroxide represented by [A n-] x / n ⁇ zH 2 O
- the M 2+ is one or more of Mg 2+ , Ca 2+ , Fe 2+ , Ni 2+ and Zn 2+
- the M 3+ is one or more of Al 3+ , Fe 3+ and Cr 3+.
- a n-is OH -, CO 3 2-, Cl -, (SO 4) zinc-based plated steel sheet characterized in that it is 2-one or more.
- the organic resin is an epoxy resin, a modified epoxy resin, a polyhydroxy polyether resin, a polyalkylene glycol-modified epoxy resin, a urethane-modified epoxy resin, and these
- a zinc-based plated steel sheet which is one or more selected from resins obtained by further modifying resins, polyester resins, urethane resins, silicone resins, and acrylic resins.
- a steel sheet obtained by plating zinc on a steel sheet by various production methods such as a hot dipping method, an electroplating method, a vapor deposition method, and a thermal spraying method is generically called a zinc-based plated steel plate.
- both the hot dip galvanized steel sheet which has not been alloyed and the galvannealed steel sheet which has been subjected to the alloying process are included in the galvanized steel sheet.
- the present invention even when the surface pressure at the time of press molding increases, the sliding resistance at the risk of cracking at the time of press molding is small, the surface pressure is also high and the portion where plating adheres to the mold is assumed. Can obtain a galvanized steel sheet having excellent press formability.
- Schematic front view showing the dynamic friction coefficient measuring device Schematic perspective view showing bead shape and dimensions in FIG. 1 (bead shape 1) Schematic perspective view showing bead shape and dimensions in FIG. 1 (bead shape 2)
- the frictional resistance was reduced by suppressing the contact between the galvanized layer and the mold.
- the amount of wear of the film increases, so that a sufficient effect cannot be obtained if the sliding distance exceeds a certain amount.
- the surface of the zinc-based plated steel sheet has an organic-inorganic composite film containing an organic resin and a crystalline layered material.
- the lubrication mechanism of the crystalline layered material contained in the organic-inorganic composite film is not clear, it can be considered as follows. During sliding, a shear stress is generated on the surface due to the adhesive force between the mold and the plating. The presence of the crystalline layered material between the plating and the mold absorbs the shear deformation stress generated on the surface due to slip deformation of the crystalline layered material. And even after the crystalline layered material is worn out from the zinc-based plating surface layer, it exhibits the effect of adhering to the mold and reducing the frictional resistance. Can be obtained. Further, by containing an organic resin in the organic-inorganic composite film, it becomes possible to coat the crystalline layered material with a uniform thickness on the steel sheet surface. For the reasons described above, in the present invention, an organic-inorganic composite film containing an organic resin and a crystalline layered material is provided on the surface of a zinc-based plated steel sheet. This is the most important requirement in the present invention.
- the thickness of the organic-inorganic composite film containing the organic resin and the crystalline layered material is an average film thickness as a thickness when observed by SEM from a cross section. 0.10 ⁇ m or more and 2.0 ⁇ m or less. If the average film thickness is less than 0.10 ⁇ m, it is difficult to form a uniform film on the surface of the steel sheet. On the other hand, when the average film thickness exceeds 2.0 ⁇ m, there is a concern that spot weldability, which is important in automobile production, is deteriorated.
- the thickness of the organic-inorganic composite film can be measured from the result of observing a cross section processed with FIB with a very low acceleration SEM.
- identification of the crystal structure as to whether the crystalline layered material is crystalline can be performed by thin film X-ray diffraction.
- the crystalline layered product contains 0.5 parts by weight or more as solid content with respect to 100 parts by weight of organic resin solid content. If the amount is less than 0.5 part by weight, a sufficient effect cannot be exhibited because there are few crystal layered substances that come into contact with the mold when sliding.
- the crystalline layered material is a crystal in which a plate-like covalently bonded crystal is laminated with a relatively weak bond such as intermolecular force, hydrogen bond, electrostatic energy, etc. in the unit crystal lattice. is there.
- the layered double hydroxide whose structure can be represented by [M 2 + 1-X M 3+ X (OH) 2 ] [A n ⁇ ] x / n ⁇ zH 2 O is a positively charged plate
- a negatively charged anion binds with electrostatic energy to keep the electrical balance against divalent and trivalent metal hydroxides, and has a layered crystal structure because it is laminated in layers. It is preferable to use as a product.
- M 2+ is preferably one or more of Mg 2+ , Ca 2+ , Fe 2+ , Ni 2+ , Zn 2+ , Pb 2+ , and Sn 2+ .
- Mg 2+ , Ca 2+ , Fe 2+ , Ni 2+ , and Zn 2+ have been confirmed as natural or artificially generated layered double hydroxide species and can exist stably as layered double hydroxides. Therefore, it is more preferable.
- Al 3+ , Fe 3+ , Cr 3+ , 3 / 4Zr 4+ , and Mo 3+ are preferable.
- Al 3+ , Fe 3+ , and Cr 3+ are more preferable because they have been confirmed as naturally or artificially generated layered double hydroxide species and can exist stably as layered double hydroxides. .
- a method for producing a crystalline layered product will be described.
- a method of generating a layered double hydroxide, which is a kind of crystalline layered material, in powder form is shown.
- the method of dripping an anion containing solution to the aqueous solution containing a cation is mentioned.
- an aqueous solution containing one or more anions At this time, a 2.0 mol-NaOH solution is dropped to adjust the solution so that the pH of the reaction suspension is 10 ⁇ 0.1.
- the divalent cation and the trivalent cation present in the reaction suspension are present in a colloidal form as a hydroxide.
- OH ⁇ , F ⁇ , CO 3 2 ⁇ , Cl ⁇ , Br ⁇ , (C 2 O 4 ) 2 ⁇ , I ⁇ , (NO 3 ) ⁇ , (SO 4 ) 2 ⁇ , (BrO) are contained in the liquid.
- the powdery layered double hydroxide obtained as described above and an organic resin are appropriately blended and stirred to prepare a coating composition.
- a paint disperser sand grinder
- the stirring time is appropriately adjusted. In order to sufficiently disperse the powdery layered double hydroxide in the organic solvent, the stirring time is preferably 30 minutes or more.
- organic resins examples include epoxy resins, modified epoxy resins, polyhydroxy polyether resins, polyalkylene glycol-modified epoxy resins, urethane-modified epoxy resins, and resins obtained by further modifying these resins, polyester resins, urethane resins, silicone resins, acrylic resins It is appropriate that one or more are selected from the above.
- an epoxy resin is used as a base, the molecular weight of which is appropriately optimized with the aim of improving processability, and a resin part modified with urethane, polyester, amine, etc. desirable.
- organic coloring pigments for example, condensed polycyclic organic pigments, phthalocyanine organic pigments
- coloring dyes for example, water-soluble azo metal dyes
- inorganic pigments for example, oxidation
- titanium coupling agents eg, titanium coupling agents
- the means for applying the obtained coating composition to the steel sheet surface is not particularly limited.
- a roll coater is preferably used.
- a dryer, hot air furnace, high frequency induction heating furnace, infrared furnace or the like can be used, but a high frequency induction heating furnace is particularly preferable from the viewpoint of corrosion resistance.
- the heat treatment is desirably performed in the range of 50 to 350 ° C., preferably 80 to 250 ° C. at the ultimate plate temperature. If the heating temperature is less than 50 ° C., a large amount of the solvent remains in the film, resulting in insufficient corrosion resistance.
- the additive element components other than Al are not particularly limited. That is, even if Pb, Sb, Si, Sn, Mg, Mn, Ni, Ti, Li or the like other than Al is contained or added, the effect of the present invention is not impaired.
- the layered double hydroxide is an aqueous solution containing any one or more of the divalent cations (M 2+ ) shown in Table 1 and any one or more of the trivalent cations (M 3+ ) (in Table 1, It refine
- the coating composition to be the organic-inorganic composite film formed on the surface uses the organic resin shown in Table 2 as the resin composition, and the layered double hydroxide produced by the above method is appropriately blended as shown in Table 3. The mixture was stirred for 45 minutes using a paint disperser (sand grinder) to prepare a paint composition.
- a paint disperser sand grinder
- An alloyed hot-dip galvanized film was formed by a conventional method on a cold-rolled steel sheet having a thickness of 0.7 mm as a steel sheet for coating film base, and further subjected to temper rolling.
- a hot dip galvanized film and an electrogalvanized film were formed by a conventional method.
- the coating composition was applied with a roll coater and baked (heated and dried) at a baking temperature of 140 ° C. shown in Table 3.
- the film thickness of the organic-inorganic composite film was adjusted by the solid content (heating residue) of the coating composition or the coating conditions (rolling force of the roll, rotational speed, etc.).
- the layered double hydroxide was identified.
- the friction coefficient was measured and the mold caulking property was evaluated to evaluate the sliding characteristics.
- each measuring method and identification method are as follows.
- Matched cards were: A) Magnesium Aluminum Hydroxide Carbonate Hydrate ICDD card reference code: 01-089-0460 [Mg 0.667 Al 0.333 (OH) 2 ] [CO 3 2 ⁇ ] 0.167 ⁇ 0.5H 2 O B) Zinc Aluminum Carbonate Hydrate ICDD card reference code: 00-048-1021 [Zn 0.71 Al 0.29 (OH) 2 ] [CO 3 2 ⁇ ] 0.145 ⁇ H 2 O C) Iron Carbonate Hydrate ICDD card reference code: 00-050-1380 [Fe 0.67 Fe 0.33 (OH) 2 ] [CO 3 2 ⁇ ] 0.145 ⁇ 0.33H 2 O D) Iron Nickel Sulfate Hydroxide Hydrate ICDD card reference code: 00-042-0573 [Ni 0.75 Fe 0.25 (OH) 2 ] [SO 4 2 ⁇ ] 0.125 ⁇ 0.5H 2 O E) Magnesium Aluminum Hydroxide Hydrate ICDD card reference code: 00-038-0478 [Mg 0.75 Al 0.25 (OH
- FIG. 1 is a schematic front view showing a friction coefficient measuring apparatus.
- a friction coefficient measurement sample 1 collected from a test material is fixed to a sample table 2, and the sample table 2 is fixed to the upper surface of a slide table 3 that can move horizontally.
- a 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, and the pressing load N applied to the friction coefficient measurement sample 1 by the bead 6 is measured by pushing it up.
- a first load cell 7 is attached to the slide table support 5.
- a second load cell 8 is attached to one end of the slide table 3 in order to measure a sliding resistance force F for moving the slide table 3 in the horizontal direction with the pressing force applied.
- the cleaning oil Preton R352L for press made by Sugimura Chemical Co., Ltd. as a lubricating oil was applied to the surface of the friction coefficient measurement sample 1 and tested.
- FIG. 2 is a schematic perspective view showing the shape and dimensions of the bead used (bead shape 1 hereinafter).
- the bead 6 slides with its lower surface pressed against the surface of the friction coefficient measurement sample 1.
- the bead 6 shown in FIG. 2 has a width of 10 mm, a length of 12 mm in the sliding direction of the sample, and a lower portion at both ends in the sliding direction is formed by a curved surface with a curvature of 4.5 mmR. It has a plane with a direction length of 3 mm.
- FIG. 3 is a schematic perspective view showing the shape and dimensions of the bead used (bead shape 2 hereinafter).
- the bead 6 slides with its lower surface pressed against the surface of the friction coefficient measurement sample 1.
- the shape of the bead 6 shown in FIG. 3 is 10 mm in width, 69 mm in the sliding direction length of the sample, the lower part at both ends in the sliding direction is configured with a curved surface having a curvature of 4.5 mmR, and the lower surface of the bead to which the sample is pressed is 10 mm in width and sliding It has a plane with a direction length of 60 mm.
- the coefficient of friction was measured under three conditions of 400, 1200, and 1600 kgf at room temperature (25 ° C.) so as to obtain a surface pressure assuming press forming of a high-strength steel plate.
- the combinations of bead shape, pressing load conditions, and drawing speed are as follows.
- Condition 1 Bead shape 1 Pressing load 400 kgf Pulling speed 100 cm / min
- Condition 2 Bead shape 1 Pressing load 1200 kgf Pulling speed 100 cm / min
- Condition 3 Bead shape 1 Pressing load 1600 kgf Pulling speed 100 cm / min
- Condition 4 Bead shape 2 Pressing load 400 kgf Pulling speed 20 cm / min
- test conditions were the same as those in the above conditions 1 to 3 so that the surface pressure was assumed to be high-strength steel sheet press forming as in the above-described 3) coefficient of friction measurement method.
- the test results obtained above are shown in Table 3 together with the conditions.
- No1 is a comparative example in which no crystalline layered material is contained. High coefficient of friction and inferior moldability.
- Nos. 2 to 27 are examples of the present invention containing an organic resin and a crystalline layered product. Compared with the comparative example of No1, the friction coefficient is low and the mold caulking property is good.
- No. 28 is a comparative example in which no crystalline layered material is contained. High friction coefficient.
- Nos. 29 to 38 are examples of the present invention containing an organic resin and a crystalline layered product. Compared with the comparative example of No. 28, the friction coefficient is low.
- No39 is a comparative example containing no crystalline layered material. High coefficient of friction and inferior moldability.
- Nos. 40 to 49 are examples of the present invention containing an organic resin and a crystalline layered product. Compared with the comparative example of No39, the friction coefficient is low and the mold caulking property is good.
- the galvanized steel sheet of the present invention is excellent in press formability, it can be applied in a wide range of fields mainly for automobile body applications that require difficult-to-form materials.
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Abstract
Description
か、電解処理を行う、または上記水溶液を塗布することにより、亜鉛系めっき鋼板表面に、P酸化物を主体とした酸化膜を形成して、プレス成形性および化成処理性を向上させる技術を開示している。
そこで、本発明者らは、上記の課題を解決すべく、鋭意研究を重ねた。その結果、摺動性を飛躍的に改善するためには、亜鉛系めっき鋼板の表面に結晶性層状物を被覆した皮膜を形成することが有効であることを見出した。
[1] 表面に有機樹脂および結晶性層状物を含有する有機無機複合皮膜を有し、該有機無機複合皮膜は、平均膜厚が0.10~2.0μmであり、有機樹脂固形分100重量部に対して、固形分として0.5重量部以上の結晶性層状物を含有することを特徴とする亜鉛系めっき鋼板。
[2]前記[1]において、前記結晶性層状物は[M2+ 1−XM3+ X(OH)2][An−]x/n・zH2Oで示される層状複水酸化物であり、前記M2+はMg2+、Ca2+、Fe2+、Ni2+、Zn2+、Pb2+、Sn2+の1種または2種以上であり、前記M3+はAl3+、Fe3+、Cr3+、3/4Zr4+、Mo3+の1種または2種以上であり、前記An−はOH−、F−、CO3 2−、Cl−、Br−、(C2O4)2−、I−、(NO3)−、(SO4)2−、(BrO3)−、(IO3)−、(V10O28)6−、(Si2O5)2−、(ClO4)−、(CH3COO)−、[C6H4(CO2)2]2−、(C6H5COO)−、[C8H16(CO2)2]2−、n(C8H17SO4)−、n(C12H25SO4)−、n(C18H37SO4)−、SiO4 4−の1種または2種以上であることを特徴とする亜鉛系めっき鋼板。
[3]前記[1]において、前記結晶性層状物は[M2+ 1−XM3+ X(OH)2][An−]x/n・zH2Oで示される層状複水酸化物であり、前記M2+はMg2+、Ca2+、Fe2+、Ni2+、Zn2+の1種または2種以上であり、前記M3+はAl3+、Fe3+、Cr3+の1種または2種以上であり、An−がOH−、CO3 2−、Cl−、(SO4)2−の1種または2種以上であることを特徴とする亜鉛系めっき鋼板。
[4]前記[1]~[3]のいずれかにおいて、前記有機樹脂が、エポキシ樹脂、変性エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、ポリアルキレングリコール変性エポキシ樹脂、ウレタン変性エポキシ樹脂、及び、これらの樹脂をさらに変性させた樹脂、ポリエステル樹脂、ウレタン樹脂、シリコン樹脂、アクリル樹脂から選ばれる1種または2種以上であることを特徴とする亜鉛系めっき鋼板。なお、本発明においては、例えば、溶融めっき法、電気めっき法、蒸着めっき法、溶射法などの各種の製造方法により鋼板上に亜鉛をめっきした鋼板を総称して亜鉛系めっき鋼板と呼称する。また、合金化処理を施していない溶融亜鉛めっき鋼板、合金化処理を施す合金化溶融亜鉛めっき鋼板のいずれも亜鉛系めっき鋼板に含まれる。
また、有機無機複合皮膜中に有機樹脂を含有することで、鋼板表面に均一な厚さで結晶性層状物を被覆することが可能となる。
以上の理由から、本発明においては、亜鉛系めっき鋼板の表面に有機樹脂および結晶性層状物を含有する有機無機複合皮膜を有することとする。そして、これは本発明において最も重要な要件である。
[M2+ 1−XM3+ X(OH)2][An−]x/n・zH2Oで示される層状複水酸化物であることは、X線回折で同定することができ、上記式で表すことが可能な物質は層状結晶となることが知られている。
なお、得られた粉状の物質が層状化合物であるかどうかは、XRD回折により確認することができる。
加熱乾燥(焼き付け)処理は、ドライヤー、熱風炉、高周波誘導加熱炉、赤外線炉などを用いることができるが、耐食性の観点からは高周波誘導加熱炉が特に好ましい。加熱処理は、到達板温で50~350℃、好ましくは80℃~250℃の範囲で行うことが望ましい。加熱温度が50℃未満では皮膜中の溶媒が多量に残り、耐食性が不十分となる。また、加熱温度が350℃を超えると非経済的であるばかりでなく、皮膜に欠陥が生じて耐食性が低下するおそれがある。
以上により、表面に有機樹脂および結晶性層状物を含有する有機無機複合皮膜を有する亜鉛系めっき鋼板が得られる。
層状複水酸化物は、表1に示す2価のカチオン(M2+)のいずれか一種類以上と、3価のカチオン(M3+)のいずれか一種類以上とを含む水溶液(表1中、水溶液1組成)中に、無機アニオン又は有機アニオン(An−)のうちいずれか1種類以上のアニオンを含む水溶液(表1中、水溶液2組成)を滴下することで精製した。この際、反応懸濁液のpHが10±0.1となるように2.0モル−NaOH溶液を滴下して溶液を調整した。次いで、得られた沈殿物をろ過し、乾燥して粉状の層状複水酸化物を得た。なお、XRD回折により層状複水酸化物であることを確認した。
上記により得られた各種めっき鋼板の表面をアルカリ脱脂処理、水洗乾燥した後、上記塗料組成物をロールコータにより塗布し、表3に示す焼き付け温度:140℃で焼き付け(加熱乾燥)した。なお、有機無機複合皮膜の膜厚は、塗料組成物の固形分(加熱残分)または塗布条件(ロールの圧下力、回転速度など)により調整した。
FIBを用いて皮膜の断面を45°にスパッタリングし、極低加速SEMで断面を観察し、10点を測定した平均値をその皮膜の膜厚とした。
X線回折法により結晶性の層状複水酸化物の存在を確認した。Cu−Kα線を用いX線回折法により得られるピークをICDDカードと照合して層状複水酸化物を同定した。合致したカードは下記であった。
ア)Magnesium Aluminum Hydroxide Carbonate Hydrate
ICDDカードリファレンスコード:01−089−0460
[Mg0.667Al0.333(OH)2][CO3 2−]0.167・0.5H2O
イ)Zinc Aluminum Carbonate Hydroxide Hydrate
ICDDカードリファレンスコード:00−048−1021
[Zn0.71Al0.29(OH)2][CO3 2−]0.145・H2O
ウ)Iron Carbonate Hydroxide Hydrate
ICDDカードリファレンスコード:00−050−1380
[Fe0.67Fe0.33(OH)2][CO3 2−]0.145・0.33H2O
エ)Iron Nickel Sulfate Hydroxide Hydrate
ICDDカードリファレンスコード:00−042−0573
[Ni0.75Fe0.25(OH)2][SO4 2−]0.125・0.5H2O
オ)Magnesium Aluminum Hydroxide Hydrate
ICDDカードリファレンスコード:00−038−0478
[Mg0.75Al0.25(OH)2][OH−]0.25・0.5H2O
カ)Magnesium Iron Oxide Chloride Hydroxide Hydrate
ICDDカードリファレンスコード:00−020−0500
[Mg0.75Fe0.25(OH)2][Cl−]0.25・0.5H2O
キ)Calcium Aluminum Hydroxide Chloride Hydrate
ICDDカードリファレンスコード:00−035−0105
[Ca0.67Al0.33(OH)2][Cl−]0.33・0.67H2O
ク)Magnesium Chromium Carbonate Hydroxide Hydrate
ICDDカードリファレンスコード:00−045−1475
[Mg0.67Cr0.33(OH)2][CO3 2−]0.157・0.5H2O
ケ)Iron Aluminum Oxide Carbonate Hydroxide Hydrate
ICDDカードリファレンスコード:00−051−1527
[Fe0.67Al0.33(OH)2][CO3 2−]0.157・0.5H2O
コ)Nickel Aluminum Oxide Carbonate Hydroxide Hydrate
ICDDカードリファレンスコード:00−015−0087
[Ni0.67Al0.33(OH)2][CO3 2−,OH−]0.157・0.5H2O
プレス成形性(特に絞り・流入部における成形性)を評価するために、各供試材の動摩擦係数を以下のようにして測定した。図1は摩擦係数測定装置を示す概略正面図である。同図に示すように、供試材から採取した摩擦係数測定用試料1が試料台2に固定され、試料台2は、水平移動可能なスライドテーブル3の上面に固定されている。スライドテーブル3の下面には、これに接したローラ4を有する上下動可能なスライドテーブル支持台5が設けられ、これを押し上げることによりビード6による摩擦係数測定用試料1への押し付け荷重Nを測定するための第1ロードセル7がスライドテーブル支持台5に取り付けられている。上記押し付け力を作用させた状態でスライドテーブル3を水平方向へ移動させるための摺動抵抗力Fを測定するために第2ロードセル8が、スライドテーブル3の一方の端部に取り付けられている。なお、潤滑油としてスギムラ化学社製のプレス用洗浄油プレトンR352Lを摩擦係数測定用試料1の表面に塗布して試験を行った。
ビード形状および押し付け荷重条件、引き抜き速度の組み合わせは以下の通りである。
条件1: ビード形状1 押し付け荷重400kgf 引き抜き速度100cm/min
条件2: ビード形状1 押し付け荷重1200kgf 引き抜き速度100cm/min
条件3: ビード形状1 押し付け荷重1600kgf 引き抜き速度100cm/min
条件4: ビード形状2 押し付け荷重400kgf 引き抜き速度20cm/min
動摩擦係数に加え、純亜鉛系めっき鋼板では、摺動距離が長い部位において金型へめっきが付着し摺動抵抗が増加する型カジリが問題となる。そこで、図1に示した摩擦係数測定装置を用いて,摺動試験を50回繰り返し実施し、摩擦係数が0.01以上増加した繰り返し数を型カジリ発生の繰り返し数として、型カジリ性の評価を実施した。ここで、50回繰り返し摺動試験を実施しても摩擦係数の上昇が認められない場合には、50回以上とした。試験条件は上記3)摩擦係数の測定方法と同様に高強度鋼板のプレス成形を想定した面圧になるよう上記の条件1~条件3で実施した。
以上より得られた試験結果を条件と併せて表3に示す。
溶融亜鉛めっき鋼板(GI)を用いた場合No1は結晶性層状物が含有されていない比較例である。摩擦係数が高く、型カジリ性が劣っている。No2~27は有機樹脂および結晶性層状物が含有されている本発明例である。No1の比較例と比較すると摩擦係数が低く、型カジリ性が良好である。
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
N 押付荷重
F 摺動抵抗力
Claims (4)
- 表面に有機樹脂および結晶性層状物を含有する有機無機複合皮膜を有し、該有機無機複合皮膜は、平均膜厚が0.10~2.0μmであり、有機樹脂の固形分100重量部に対して、固形分として0.5重量部以上の結晶性層状物を含有することを特徴とする亜鉛系めっき鋼板。
- 前記結晶性層状物は[M2+ 1−XM3+ X(OH)2][An−]x/n・zH2Oで示される層状複水酸化物であり、前記M2+はMg2+、Ca2+、Fe2+、Ni2+、Zn2+、Pb2+、Sn2+の1種または2種以上であり、前記M3+はAl3+、Fe3+、Cr3+、3/4Zr4+、Mo3+の1種または2種以上であり、前記An−はOH−、F−、CO3 2−、Cl−、Br−、(C2O4)2−、I−、(NO3)−、(SO4)2−、(BrO3)−、(IO3)−、(V10O28)6−、(Si2O5)2−、(ClO4)−、(CH3COO)−、[C6H4(CO2)2]2−、(C6H5COO)−、[C8H16(CO2)2]2−、n(C8H17SO4)−、n(C12H25SO4)−、n(C18H37SO4)−、SiO4 4−の1種または2種以上であることを特徴とする請求項1に記載の亜鉛系めっき鋼板。
- 前記結晶性層状物は[M2+ 1−XM3+ X(OH)2][An−]x/n・zH2Oで示される層状複水酸化物であり、前記M2+はMg2+、Ca2+、Fe2+、Ni2+、Zn2+の1種または2種以上であり、前記M3+はAl3+、Fe3+、Cr3+の1種または2種以上であり、An−がOH−、CO3 2−、Cl−、(SO4)2−の1種または2種以上であることを特徴とする請求項1に記載の亜鉛系めっき鋼板。
- 前記有機樹脂が、エポキシ樹脂、変性エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、ポリアルキレングリコール変性エポキシ樹脂、ウレタン変性エポキシ樹脂、及び、これらの樹脂をさらに変性させた樹脂、ポリエステル樹脂、ウレタン樹脂、シリコン樹脂、アクリル樹脂から選ばれる1種または2種以上であることを特徴とする請求項1~3のいずれかに記載の亜鉛系めっき鋼板。
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EP (1) | EP2505351A4 (ja) |
JP (1) | JP5696445B2 (ja) |
KR (1) | KR20120094066A (ja) |
CN (1) | CN102630199B (ja) |
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WO2013156541A1 (en) * | 2012-04-17 | 2013-10-24 | Chemetall Gmbh | Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide |
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JP5838542B2 (ja) * | 2010-09-29 | 2016-01-06 | Jfeスチール株式会社 | 冷延鋼板の製造方法 |
JP5750852B2 (ja) * | 2010-09-29 | 2015-07-22 | Jfeスチール株式会社 | 冷延鋼板 |
TWI448649B (zh) * | 2012-06-08 | 2014-08-11 | Taiwan Sakura Corp | 防銹瓦斯爐頭及其製造方法 |
KR101406650B1 (ko) | 2012-08-31 | 2014-06-11 | 주식회사 포스코 | 미소크랙이 억제된 열간 프레스 성형품 |
KR101568496B1 (ko) * | 2013-12-20 | 2015-11-11 | 주식회사 포스코 | 열간 프레스 성형용 아연도금강판 및 그 제조방법 |
EP3283575B1 (de) * | 2015-04-17 | 2019-08-14 | Akzo Nobel Coatings International B.V. | Beschichtungsverfahren |
CN110158095B (zh) * | 2019-06-28 | 2021-11-30 | 辽宁工业大学 | 一种镀锌钢表面ldh的制备方法 |
JP7375794B2 (ja) * | 2020-09-09 | 2023-11-08 | Jfeスチール株式会社 | 鋼板 |
JP7375795B2 (ja) * | 2020-09-09 | 2023-11-08 | Jfeスチール株式会社 | プレス成形品の製造方法 |
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US20120321908A1 (en) | 2012-12-20 |
CN102630199B (zh) | 2016-02-24 |
CN102630199A (zh) | 2012-08-08 |
EP2505351A4 (en) | 2016-01-13 |
EP2505351A1 (en) | 2012-10-03 |
TWI457464B (zh) | 2014-10-21 |
TW201126020A (en) | 2011-08-01 |
JP2011131586A (ja) | 2011-07-07 |
KR20120094066A (ko) | 2012-08-23 |
JP5696445B2 (ja) | 2015-04-08 |
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