WO2012043511A1 - 冷延鋼板 - Google Patents

冷延鋼板 Download PDF

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Publication number
WO2012043511A1
WO2012043511A1 PCT/JP2011/071956 JP2011071956W WO2012043511A1 WO 2012043511 A1 WO2012043511 A1 WO 2012043511A1 JP 2011071956 W JP2011071956 W JP 2011071956W WO 2012043511 A1 WO2012043511 A1 WO 2012043511A1
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WIPO (PCT)
Prior art keywords
cold
rolled steel
steel sheet
organic
resin
Prior art date
Application number
PCT/JP2011/071956
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English (en)
French (fr)
Inventor
克弥 星野
大塚　真司
孝宜 矢野
三好　達也
Original Assignee
Ｊｆｅスチール株式会社
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Publication date
Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to MX2013003377A priority Critical patent/MX340516B/es
Priority to CN2011800465516A priority patent/CN103124636A/zh
Priority to KR1020137007587A priority patent/KR101537176B1/ko
Priority to US13/824,772 priority patent/US9321246B2/en
Priority to EP11829064.2A priority patent/EP2623312A4/en
Priority to CA 2811656 priority patent/CA2811656C/en
Publication of WO2012043511A1 publication Critical patent/WO2012043511A1/ja

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • 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
    • B32B15/06—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 natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/10—Groups 5 or 15
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the present invention relates to a cold-rolled steel sheet having excellent press formability.
  • Cold-rolled steel sheets are widely used in a wide range of fields centering on automobile body applications. In such an application, it is subjected to press molding for use.
  • the usage ratio of high-strength steel sheets tends to increase for the purpose of reducing vehicle body weight.
  • the surface pressure increases during press forming as the base metal strength increases.
  • Patent Document 1 describes a technique for forming a lubricating film containing an alkali metal borate and a mixture of zinc stearate as a lubricant and a wax on a steel plate.
  • Patent Document 2 describes a technique in which lithium silicate is used as a film component, and a product obtained by adding wax and metal soap as a lubricant to the film component is formed on a steel plate.
  • Patent Document 3 describes a lubricated steel sheet excellent in continuity formation by high surface pressure processing, in which a polyurethane resin having a silanol group or a hydroxyl group is formed in a thickness of 1 to 15 ⁇ m.
  • Patent Documents 1 to 3 although lubricity is exhibited by the contained lubricant and the like, the required characteristics are not satisfied particularly in a portion having a high surface pressure such as a high-strength cold-rolled steel sheet.
  • the present invention provides a cold-rolled steel sheet having excellent press formability, in which it is difficult to generate mold galling and can be precisely formed in difficult-to-form materials such as high-strength steel sheets whose surface pressure increases during press forming. With the goal.
  • the lubricity of the lubrication film depends largely on the lubrication performance of the lubricant in the film, and it is considered that a new lubricant needs to be developed. Accordingly, the present inventors have intensively researched and devised a technique that utilizes deformation caused by slippage between crystalline layers as a lubrication mechanism. If the slip between the layers is generated with a low stress, it is expected that even when a high pressing pressure (surface pressure) slips, the resistance is small and excellent lubricity is exhibited. In discovering a specific crystalline layered material, a substance in which the layers are bonded with weak bonding force such as intermolecular force, hydrogen bond, electrostatic energy, etc. was extracted.
  • the present invention has been made based on the above knowledge, and the gist thereof is as follows.
  • It has an organic-inorganic composite film containing an organic resin and a crystalline layered material on the surface, and the organic-inorganic composite film has an average film thickness of 0.10 to 2.0 ⁇ m and is 100 parts by weight of organic resin solid content
  • a cold-rolled steel sheet comprising 0.5 part by weight or more of a crystalline layered material as a solid content.
  • the crystalline layered product 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 Mg 2+ , Ca 2+ , Fe 2+ , Ni 2+ , Zn 2+ , Pb 2+ , Sn 2+
  • the M 3+ is Al 3+, Fe 3+, Cr 3+ , and a 3 / 4Zr 4+, 1 or more kinds 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 ) - , (CH 3 COO)
  • the crystalline layered product 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+
  • the M 3+ is Al 3+ , Fe 3+.
  • it is one or more of Cr 3+, wherein a n- is OH -, CO 3 2-, Cl -, and wherein the at (SO 4) 2-one or more Cold rolled steel sheet.
  • the organic resin is one or more selected from an epoxy resin, a polyhydroxy polyether resin, a polyester resin, a urethane resin, a silicon resin, and an acrylic resin.
  • a cold-rolled steel sheet characterized by
  • FIG. 1 is a schematic front view showing a friction coefficient measuring apparatus.
  • FIG. 2 is a schematic perspective view (bead shape 1) showing a first shape / dimension of the bead 6 in FIG.
  • FIG. 3 is a schematic perspective view (bead shape 2) showing a second shape / dimension of the bead 6 in FIG.
  • the cold-rolled steel sheet of the present invention has an organic-inorganic composite film containing an organic resin and a crystalline layered material on the surface of the cold-rolled steel sheet.
  • the organic-inorganic composite film has an average film thickness of 0.10 to 2.0 ⁇ m, It contains 0.5 parts by weight or more of a crystalline layered product as a solid content with respect to 100 parts by weight of the resin solid content. This is the most important requirement of the cold rolled steel sheet of the present invention.
  • the mechanism of lubrication of the crystalline layered material contained in the organic-inorganic composite film can be considered as follows.
  • a shear stress is generated on the surface of the cold-rolled steel sheet due to the adhesion between the mold and the surface of the cold-rolled steel sheet.
  • the crystalline layered material exists between the cold-rolled steel sheet and the mold, the crystalline layered material is deformed by slippage between layers and absorbs shear deformation stress generated on the surface.
  • the crystalline layered material adheres to the mold and reduces the frictional resistance between the mold and the cold-rolled steel plate. Therefore, sufficient effects can be obtained even under high surface pressure conditions assuming a high-strength steel sheet.
  • it is effective from the viewpoint of adhesion at the time of coating that the organic-inorganic composite film contains an organic resin, and the surface of the cold-rolled steel sheet can be coated with a crystalline layered material with a uniform thickness. It becomes.
  • the thickness of the organic-inorganic composite film containing the organic resin and the crystalline layered material is the average film thickness when the cross-section is observed with an SEM. 0.10 ⁇ m to 2.0 ⁇ m. If the average film thickness is less than 0.10 ⁇ m, it is difficult to form a uniform film on the surface of the cold-rolled steel sheet. On the other hand, if the average film thickness exceeds 2.0 ⁇ m, there is a concern that spot weldability, which is important in automobile production, is reduced.
  • the thickness of the organic-inorganic composite film can be measured from the result of observing a cross section processed with FIB with an SEM having an acceleration voltage of 5 kV or less. In addition, 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 material contains 0.5 parts by weight or more as a solid content with respect to 100 parts by weight of the organic resin solid content.
  • the solid content of the crystalline layered product is less than 0.5 parts by weight, a sufficient effect cannot be exhibited because there are few crystalline layered products that come into contact with the mold when the mold and the cold-rolled steel sheet slide.
  • 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 It has a layered crystal structure because negatively charged anions are bonded to each other by electrostatic energy in order to maintain an electrical balance with the divalent and trivalent metal hydroxides, and are laminated in layers.
  • 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+ , Zn 2+ have been confirmed as naturally or artificially generated layered double hydroxide species, and are stable as layered double hydroxides. It is more preferable because it can exist.
  • M 3+ is preferably one or more of Al 3+ , Fe 3+ , Cr 3+ , 3 / 4Zr 4+ and Mo 3+ .
  • Al 3+ , Fe 3+ , and Cr 3+ have been confirmed as layered double hydroxide species generated naturally or artificially and can exist stably as layered double hydroxides. More preferable.
  • interlayer anions of the layered double hydroxide species have been confirmed to be incorporated as interlayer anions of the layered double hydroxide species, and can exist as layered double hydroxides.
  • OH -, CO 3 2-, Cl -, (SO 4) 2- is easily capture an interlayer anions as compared to the other anions of the layered double hydroxide species when formed on the surface of the cold rolled steel sheet Since the film can be formed in a short time, it can be more suitably used as an anion.
  • a method for generating the organic-inorganic composite coating on the surface of the cold rolled steel sheet will be described.
  • 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 of divalent cations (M 2+ ) and one or more of trivalent cations (M 3+ ) an inorganic anion or an organic anion (A n ⁇ )
  • An aqueous solution containing one or more types of anions is dropped.
  • the 2.0 mol-NaOH solution is added dropwise 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.
  • 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.
  • the organic resin one or more selected from epoxy resins, polyhydroxy polyether resins, polyester resins, urethane resins, silicone resins, and acrylic resins are suitable.
  • an epoxy resin is used as a base, the molecular weight is appropriately optimized for the purpose of improving processability, and a part of the resin is 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 obtained coating composition is applied to the surface of the cold rolled steel sheet and baked.
  • coating the obtained coating composition on the surface of a cold-rolled steel plate the means is not specifically 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 layered double hydroxide is an aqueous solution containing any one or more of the divalent cations (M 2+ ) shown in Table 1 and one or more of the trivalent cations (M 3+ ) (Table 1).
  • the aqueous solution containing one or more of anions (inorganic aqueous anion (A n ⁇ )) (in the aqueous solution 1 composition) was purified by dropwise addition. At this time, a 2.0 mol-NaOH solution was added dropwise to adjust the solution so that the pH of the reaction suspension was 10 ⁇ 0.1. Subsequently, the obtained precipitate was filtered and dried to obtain a powdery layered double hydroxide. In addition, it confirmed that it was a layered double hydroxide by X-ray diffraction.
  • 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).
  • a cold rolled steel sheet having a thickness of 0.7 mm subjected to temper rolling was used as a steel sheet for the base of the coating film.
  • the surface of the cold-rolled steel sheet obtained as described above is subjected to alkaline degreasing treatment, washed with water and dried, and then coated with the above-mentioned coating composition with a roll coater, and baked at 140 ° C. as shown in Table 3 (heated and dried). did.
  • 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.).
  • each measuring method and identification method are as follows.
  • 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 a first shape / dimension of the used bead 6 (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 of the sliding direction is formed by a curved surface with a curvature of 4.5 mmR. It has a 3mm long plane.
  • FIG. 3 is a schematic perspective view showing a second shape / dimension of the used bead 6 (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 wide, 69 mm long in the sliding direction of the sample, and the lower part of both ends of the sliding direction is a curved surface having a curvature of 4.5 mmR. It has a flat surface with a length of 60 mm.
  • the dynamic friction coefficient was measured under three conditions of a pressing load N 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.
  • Condition 1 Bead shape 1 Press load 400kgf Pull-out speed 100cm / min
  • Condition 2 Bead shape 1 Pressing load 1200kgf Extraction speed 100cm / min
  • Condition 3 Bead shape 1 Pressing load 1600kgf Pull-out speed 100cm / min
  • Condition 4 Bead shape 2 Pressing load 400kgf Extraction speed 20cm / min
  • No. 1 is an example in which a crystalline layered product is not contained, and is a comparative example with the present invention.
  • This comparative example has a high dynamic friction coefficient and inferior mold resistance.
  • No. Examples 2 to 27 are examples in which an organic resin and a crystalline layered material are contained, and are examples of the present invention.
  • This No. Examples of the present invention of Nos. 2 to 27 are Nos.
  • the dynamic friction coefficient is low and the mold galling resistance is good.
  • the cold-rolled steel sheet of the present invention is excellent in press formability, the cold-rolled steel sheet can be applied in a wide range of fields mainly for automobile body applications that require difficult-to-form materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Lubricants (AREA)
  • Paints Or Removers (AREA)

Abstract

　優れたプレス成形性を有する冷延鋼板を得ることを目的として、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冷延鋼板とする。そして、前記有機無機複合皮膜は、平均膜厚が0.10～2.0μmで、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。結晶性層状物としては、例えば、[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、前記An-はOH-、 CO3 2-、Cl-、 (SO4)2-の１種または２種以上であることが好ましい。

Description

冷延鋼板
　本発明は、優れたプレス成形性を有する冷延鋼板に関するものである。
　冷延鋼板は自動車車体用途を中心に広範な分野で広く利用されている。そのような用途では、プレス成形を施されて使用に供される。特に、近年のCO2排出規制強化の観点から、車体軽量化の目的で高強度鋼板の使用比率が増加する傾向にある。しかし、冷延鋼板の内、特に母材の強度が440MPaを超えるものは、母材の強度上昇に伴い、プレス成形時に面圧が上昇するため、また、冷延鋼板の硬さが金型の硬さに近づくために、冷延鋼板が金型によってかじり取られてできる型カジリとよばれる傷が発生しやすいという課題を有している。すなわち、連続プレス成形時に、金型の磨耗が激しく、成形品の外観を損なうなど、自動車の生産性に深刻な悪影響を及ぼす。
　冷延鋼板の型カジリの発生を抑制する方法としては、金型への表面処理が広く用いられる。しかし、この方法では、表面処理を施した後、金型の調整を行えない。また、この方法はコストが高いといったような問題がある。従って、冷延鋼板自身を型カジリが発生し難いものにする（耐型カジリ性を向上させる）ことが強く要請されている。
　冷延鋼板の表面に潤滑皮膜を形成させる技術も多数報告されている。特許文献１には、アルカリ金属ホウ酸塩と、潤滑剤としてのステアリン酸亜鉛とワックスとの混成物とを含有する潤滑皮膜を鋼板上に形成させる技術が記載されている。
　特許文献２には、リチウムシリケートを皮膜成分として、これに潤滑剤としてワックスと金属石鹸とを加えた物を鋼板上に形成させる技術が記載されている。
　特許文献３には、シラノール基あるいは水酸基を有するポリウレタン樹脂を1～15μmの厚さで形成させた、高面圧加工による連続性形成に優れた潤滑処理鋼板が記載されている。
特開2007-275706号公報 特開2002-307613号公報 特開2001-234119号公報
　しかしながら、特許文献１～３では、含有する潤滑剤等により潤滑性は発現するものの、特に高強度冷延鋼板のように面圧が高い部位においては要求特性を満足するものではなかった。
　本発明は、プレス成形時に面圧が上昇する高強度鋼板などの難成形材料において、型カジリが発生し難く精巧にプレス成形ができるという、優れたプレス成形性を有する冷延鋼板を提供することを目的とする。
　潤滑皮膜の潤滑性は、皮膜中の潤滑剤の潤滑性能に依存する部分が大であり、新規な潤滑剤の開発が必要であると考えられる。そこで、本発明者らは鋭意研究を重ね、潤滑の機構として結晶性層状物の層間のすべりによる変形を利用する技術を考案した。層間のすべりが低い応力で発生すれば、高い押し付け圧（面圧）でもすべりが起こる時の抵抗が少なく、優れた潤滑性を発現することが期待される。具体的な結晶性層状物を発見するに当たっては、層間が分子間力、水素結合、静電エネルギー等の弱い結合力で結合している物質を抽出した。そして、それら抽出した結晶性層状物を冷延鋼板の表面に所定量塗布することにより、摺動性が飛躍的に向上する（摺動抵抗が小さくなる）ことを見出した。更に、結晶性層状物を塗布する際の付着性の観点から、結晶性層状物を有機樹脂と混合して有機無機複合皮膜とすることが有効であることを見出した。更に、結晶性層状物としては、２価と３価の金属水酸化物がアニオンと静電エネルギーで結合した層状複水酸化物が好適であることを見出した。
　本発明は、以上の知見に基づきなされたものであり、その要旨は以下の通りである。
　［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冷延鋼板。
　［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冷延鋼板。
　［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、前記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冷延鋼板。
　［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、ポリヒドロキシポリエーテル樹脂、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冷延鋼板。
　本発明によれば、プレス成形時に面圧が上昇する場合においても、型カジリが発生しやすい部位での摺動抵抗が小さく、優れたプレス成形性を有する冷延鋼板が得られる。
図１は、摩擦係数測定装置を示す概略正面図である。 図２は、図１中のビード６の第１の形状・寸法を示す概略斜視図（ビード形状1）である。 図３は、図１中のビード６の第２の形状・寸法を示す概略斜視図（ビード形状2）である。
　本発明の冷延鋼板は、冷延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し、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。これは本発明の冷延鋼板の最も重要な要件である。
　結晶性層状物を冷延鋼板の表面に所定量塗布することにより、摺動性が飛躍的に向上する。有機無機複合皮膜に含有される結晶性層状物の潤滑のメカニズムについては、以下のように考えることができる。金型と冷延鋼板とが摺動する時、金型と冷延鋼板の表面の凝着力から冷延鋼板の表面にはせん断応力が生じる。結晶性層状物が冷延鋼板と金型との間に存在することで、結晶性層状物が層間のすべりにより変形して表面に生じるせん断変形応力を吸収する。そして、冷延鋼板が磨耗し、結晶性層状物が冷延鋼板の表面から削り取られた後にも、結晶性層状物が金型に付着し金型と冷延鋼板との間の摩擦抵抗を減少させる効果を発現するため、高強度鋼板を想定した高面圧条件においても十分な効果を得ることが可能となる。また、有機無機複合皮膜中に有機樹脂を含有することは、塗布の際の付着性の観点から有効であり、冷延鋼板の表面を均一な厚さで結晶性層状物により被覆することが可能となる。
　上記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（以下、単に有機無機複合皮膜と称する場合がある）の厚さは、断面をSEMで観察した際の厚さとして、平均膜厚が0.10μm以上2.0μm以下とする。平均膜厚が0.10μm未満では冷延鋼板の表面に均一に成膜することが困難である。一方、平均膜厚が2.0μmを超えると、自動車製造の際に重要となるスポット溶接性が低下することが懸念される。なお、有機無機複合皮膜の厚さは、FIBで加工した断面を５ｋＶ以下の加速電圧のSEMにて観察した結果から測定することができる。また、結晶性層状物が結晶性かどうかの結晶構造の同定は薄膜Ｘ線回折で行うことができる。
　また、結晶性層状物は、有機樹脂固形分100重量部に対して、固形分として0.5重量部以上を含有することとする。結晶性層状物の固形分が0.5重量部未満では、金型と冷延鋼板が摺動する時に金型と接触する結晶層状物が少ないため十分な効果を発現することができない。
　なお、本発明において、結晶性層状物とは、単位結晶格子のうち、板状の共有結合結晶が分子間力、水素結合、静電エネルギー等の比較的弱い結合で積層された結晶のことである。中でも、その構造が[M2+ 1-XM3+ X(OH)2][An-]x/n・zH2Oで表すことができる層状複水酸化物は、正に帯電した板状の２価と３価の金属水酸化物に対し、負に帯電したアニオンが電気的なバランスを保つために静電気エネルギーにより結合し層状に積層するため層状の結晶構造を有しており、本発明の結晶性層状物として用いるのに好ましい。[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。
　M2+としては、Mg2+、Ca2+、Fe2+、Ni2+、Zn2+、Pb2+、Sn2+の１種または２種以上が好ましい。中でも、Mg2+、Ca2+、Fe2+、Ni2+、Zn2+は、天然または人工的に生成した層状複水酸化物種として確認されており、層状複水酸化物として安定的に存在することが可能であるため、より好ましい。
　M3+としては、Al3+、Fe3+、Cr3+、3/4Zr4+、Mo3+の１種または２種以上が好ましい。中でも、Al3+、Fe3+、Cr3+は、天然または人工的に生成した層状複水酸化物種として確認されており、層状複水酸化物として安定的に存在することが可能であるため、より好ましい。
　An-としては、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種以上が好ましい。これらは、層状複水酸化物種の層間アニオンとしての取り込みが確認されており、層状複水酸化物として存在することが可能である。中でも、OH-、CO3 2-、Cl-、(SO4)2-は、冷延鋼板の表面に成膜する際に層状複水酸化物種の他のアニオンと比較して層間アニオンとして取り込みやすく、短時間で成膜が可能なため、アニオンとしてより好適に用いることができる。
　次いで、有機無機複合皮膜を冷延鋼板の表面に生成させる方法について説明する。まず、結晶性層状物の生成方法について説明する。ここでは、結晶性層状物の一種である層状複水酸化物を粉状に生成させる方法を一例として示す。例えば、カチオンを含有する水溶液にアニオン含有溶液を滴下する手法を挙げる。２価のカチオン（M2+）のいずれか１種類以上と、３価のカチオン（M3+）のいずれか１種類以上とを含む水溶液中に、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を滴下する。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する。反応懸濁液に存在する２価のカチオンと３価のカチオンは水酸化物としてコロイド状に存在する。ここで、液中に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-のいずれか１種以上の特定のアニオンが滴下されると、水酸化物は層状複水酸化物として沈殿する。次いで、得られた沈殿物を遠心分離機を用いて分離し、乾燥することで粉状の層状複水酸化物を得ることができる。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、Ｘ線回折により確認することができる。
　次に、上記により得られた粉状の層状複水酸化物と有機樹脂を適宜配合し、撹拌して塗料組成物を調製する。撹拌には、例えば、塗料用分散機（サンドグラインダー）を用いることができる。また、撹拌時間は、適宜調整される。有機溶媒中へ粉状の層状複水酸化物を十分に分散させるために撹拌時間は30分以上が好ましい。有機樹脂としては、エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、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種以上が適当である。特に、耐食性の観点からエポキシ系樹脂をベースとして、これに加工性を向上させることを目的として分子量を適宜最適化したものや樹脂の一部にウレタン、ポリエステル、アミンなどの変性を加えたものが望ましい。
　さらに必要に応じて、添加剤として、有機着色顔料（例えば、縮合多環系有機顔料、フタロシアニン系有機顔料など）、着色染料（例えば、水溶性アゾ系金属染料など）、無機顔料（例えば、酸化チタンなど）、導電性顔料（例えば、亜鉛、アルミニウム、ニッケルなどの金属粉末、リン化鉄、アンチモンドープ型酸化錫など）、カップリング剤（例えば、チタンカップリング剤など）、メラミン・シアヌル酸付加物などの１種または２種以上を添加することができる。
　次いで、得られた塗料組成物を冷延鋼板の表面に塗布し、焼き付けする。なお、得られた塗料組成物を冷延鋼板の表面に塗布するにあたって、その手段は特に限定しない。ロールコーターが好適に用いられる。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冷延鋼板が得られる。
　なお、成膜処理などに使用する処理液中に不純物が含まれることによりN、Pb、Na、Mn、Ba、Sr、Siなどが有機無機複合皮膜に取り込まれても、本発明の効果が損なわれるものではない。
　次に、本発明を実施例により更に詳細に説明する。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１種類以上と、３価のカチオン（M3+）のいずれか１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、Ｘ線回折により層状複水酸化物であることを確認した。
Figure JPOXMLDOC01-appb-T000001
　表面に形成する有機無機複合皮膜となる塗料組成物は、樹脂組成物として、表２に示す有機樹脂を用い、これに上記手法で生成した層状複水酸化物を表３に示すように適宜配合し、塗料用分散機（サンドグラインダー）を用いて45分間撹拌して調製した。
Figure JPOXMLDOC01-appb-T000002
　塗膜の下地用の鋼板として、調質圧延を施した板厚0.7mmの冷延鋼板を用いた。上記により得られた冷延鋼板の表面のアルカリ脱脂処理を行い、水洗乾燥した後、上記塗料組成物をロールコーターにより塗布し、表３に示すように焼き付け温度を140℃として焼き付け（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。
　以上により得られた冷延鋼板の表面の有機無機複合皮膜の平均膜厚を測定するとともに、層状複水酸化物を同定した。また、精巧なプレス成形のし易さを示すプレス成形性を評価する手法として、動摩擦係数の測定と耐型カジリ性の評価とを実施した。なお、各測定方法、同定方法は以下の通りである。
　（１）有機無機複合皮膜の平均膜厚の測定方法
　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点を抽出して測定し、その平均値をその皮膜の平均膜厚とした。
　（２）層状複水酸化物の同定方法
　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のとおりである。
　（ａ）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
　（ｂ）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
　（ｃ）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
　（ｄ）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
　（ｅ）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
　（ｆ）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
　（ｇ）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
　（ｈ）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
　（ｉ）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
　（ｊ）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
　（３）動摩擦係数の測定方法
　プレス成形性（特に絞り・流入部におけるプレス成形性）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。
　図２は、使用したビード６の第１の形状・寸法を示す概略斜視図である（以下ビード形状1）。ビード６の下面が摩擦係数測定用試料１の表面に押し付けられた状態で摺動する。図２に示すビード６の形状は幅10mm、試料の摺動方向長さ12mm、摺動方向両端の下部は曲率4.5mmRの曲面で構成され、試料が押し付けられるビード下面は幅10mm、摺動方向長さ3mmの平面を有する。
　図３は、使用したビード６の第２の形状・寸法を示す概略斜視図である（以下ビード形状2）。ビード６の下面が摩擦係数測定用試料１の表面に押し付けられた状態で摺動する。図３に示すビード６の形状は幅10mm、試料の摺動方向長さ69mm、摺動方向両端の下部は曲率4.5mmRの曲面で構成され、試料が押し付けられるビード下面は幅10mm、摺動方向長さ60mmの平面を有する。
　動摩擦係数の測定に対しては、高強度鋼板のプレス成形を想定した面圧になるよう、室温（25℃）において、押し付け荷重Ｎを400、1200、1600kgfの３条件で行った。なお試料の引抜き速度（スライドテーブル３の水平移動速度）は100cm/minまたは20cm/minである。これらの条件で、押し付け荷重Ｎと摺動抵抗力Ｆとを測定し、供試材とビード６との間の動摩擦係数μを、式：μ＝Ｆ／Ｎで算出した。
　ビード形状、押し付け荷重および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
　（４）耐型カジリ性の評価方法
　動摩擦係数に加え、冷延鋼板では、摺動距離が長い部位において冷延鋼板と金型とが凝着し摺動抵抗が増加するため型カジリが発生し易い。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、動摩擦係数が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、耐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動摩擦係数の上昇が認められない場合には、繰り返し数を50回以上とした。試験条件は上記（３）動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。
　以上により得られた試験結果を条件と併せて表３に示す。
Figure JPOXMLDOC01-appb-T000003
　表３に示す試験結果から下記事項が明らかとなった。Ｎｏ．1は結晶性層状物が含有されていない例であり、本発明との比較例である。この比較例は、動摩擦係数が高く、耐型カジリ性が劣っている。Ｎｏ．2～27は有機樹脂および結晶性層状物が含有されている例であり、本発明の一例である。このＮｏ．2～27の本発明例は、Ｎｏ．1の比較例と比較すると動摩擦係数が低く、耐型カジリ性が良好である。
　本発明の冷延鋼板はプレス成形性に優れることから、難成形材料を必要とする自動車車
体用途を中心に広範な分野で適用できる。
　１ 摩擦係数測定用試料
　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 押し付け荷重
　Ｆ 摺動抵抗力

Claims (4)

  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冷延鋼板。
  2. 　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に記載の冷延鋼板。
  3. 　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、
    　前記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に記載の冷延鋼板。
  4. 　前記有機樹脂が、エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、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のいずれか一項に記載の冷延鋼板。
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