WO2018179816A1 - 亜鉛系めっき鋼板およびその製造方法 - Google Patents

亜鉛系めっき鋼板およびその製造方法 Download PDF

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WO2018179816A1
WO2018179816A1 PCT/JP2018/003331 JP2018003331W WO2018179816A1 WO 2018179816 A1 WO2018179816 A1 WO 2018179816A1 JP 2018003331 W JP2018003331 W JP 2018003331W WO 2018179816 A1 WO2018179816 A1 WO 2018179816A1
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Prior art keywords
steel sheet
zinc
oxide layer
plated steel
galvanized steel
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PCT/JP2018/003331
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English (en)
French (fr)
Inventor
古谷　真一
松崎　晃
弘之 増岡
克弥 星野
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Ｊｆｅスチール株式会社
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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 MX2019011684A priority Critical patent/MX2019011684A/es
Priority to EP18775028.6A priority patent/EP3604615B1/en
Priority to CN201880022411.7A priority patent/CN110494591B/zh
Priority to KR1020197028627A priority patent/KR102334859B1/ko
Priority to US16/499,419 priority patent/US10907255B2/en
Publication of WO2018179816A1 publication Critical patent/WO2018179816A1/ja

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Definitions

  • the present invention relates to a galvanized steel sheet having a small sliding resistance during press forming and having excellent press formability, and a method for producing the same.
  • Zinc-based galvanized steel sheets are widely used in a wide range of fields centering on automobile body applications.
  • the zinc-based plated steel sheet is used after being subjected to press forming.
  • the zinc-based plated steel sheet has a drawback that the press formability is inferior to that of the cold-rolled steel sheet. This is because the sliding resistance of the galvanized steel sheet in the press die is larger than that of the cold-rolled steel sheet. That is, at the portion where the sliding resistance between the mold and the bead is large, the zinc-based plated steel sheet having a large sliding resistance is difficult to flow into the press mold, and the steel sheet is likely to break.
  • Patent Document 1 discloses that an oxide film mainly composed of zinc is formed by subjecting the surface of a zinc-based plated steel sheet to electrolytic treatment, immersion treatment, coating oxidation treatment, or heat treatment. A technique for improving press workability is disclosed.
  • Patent Document 2 after hot-dip galvanizing of a steel sheet, alloying is performed by heat treatment, and after temper rolling, the steel sheet is brought into contact with an acidic solution having a pH buffering action, held for a predetermined time, and then washed with water.
  • An acidic solution having a pH buffering action held for a predetermined time, and then washed with water.
  • Patent Document 3 the hot-dip galvanized steel sheet after temper rolling is brought into contact with an acidic solution having a pH buffering action, and is kept for a predetermined time in a state where a liquid film of the acidic solution is formed on the steel sheet surface, and then washed with water and dried. And the hot dip galvanized steel plate which is excellent in press formability which formed the oxide layer in the plating surface is disclosed.
  • Patent Document 4 an electrogalvanized steel sheet is brought into contact with an acidic solution having an acid buffering action or an acidic electrogalvanizing bath, and then kept for a predetermined time, followed by washing with water and drying.
  • a formed electrogalvanized steel sheet excellent in press formability is disclosed.
  • Patent Document 5 discloses the production of a zinc-based plated steel sheet in which a zinc-based plated steel sheet is brought into contact with an acidic solution, held for a predetermined time, washed with water and dried to form an oxide layer and / or a hydroxide layer on the surface.
  • a technique for obtaining excellent press formability by including an oxide colloid in an acidic solution is disclosed.
  • the present applicants contact the zinc-based plated steel sheet with an acidic solution containing a fluororesin, hold it for a predetermined time, wash with water, and dry it, so that an oxide layer and / or water containing the fluororesin is formed on the surface.
  • Patent Document 6 A technique for forming an oxide layer and obtaining a press formability far superior to that of the prior art has been proposed (Patent Document 6).
  • Japanese Patent Laid-Open No. 2-190483 Japanese Patent No. 3807341 Japanese Patent No. 4329387 JP 2005-248262 A Japanese Patent No. 5386842 JP 2016-098380 A
  • Patent Documents 1 to 5 When the techniques described in Patent Documents 1 to 5 are applied to a high-strength galvanized steel sheet, it is not always possible to obtain a sufficient effect, and even a relatively low-strength galvanized steel sheet is complicated. It was not enough to enable proper molding.
  • the present invention has been made in view of such circumstances, and is a stable and excellent press for a high-strength galvanized steel sheet and a relatively low-strength galvanized steel sheet subjected to complicated forming.
  • An object of the present invention is to provide a zinc-based plated steel sheet having formability and no harmful fumes generated during welding, and a method for producing the same.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above problem can be solved by forming an oxide layer having an average thickness of 20 nm or more and containing Zn, S and polyethylene particles on the surface of a zinc-based plated steel sheet.
  • the present invention has been completed based on the above findings, and the gist thereof is as follows.
  • An oxide layer is provided on the surface of the zinc-based plated steel sheet, the oxide layer has an average thickness of 20 nm or more, and the oxide layer contains Zn of 30 mg / m 2 or more, S 1.0 mg / m 2 or more, the average zinc-plated steel sheet having a particle diameter containing polyethylene particles is less than 5.0 .mu.m 50 mg / m 2 or more 1000 mg / m 2 or less.
  • a method for producing a galvanized steel sheet according to any one of [1] to [4] above A method for producing a zinc-based plated steel sheet, comprising bringing a zinc-based plated steel sheet into contact with an acidic solution containing 3 g / L or more of sulfate ions, 3 g / L or more of Zn ions and 0.10 g / L or more of polyethylene particles.
  • an acidic solution containing 3 g / L or more of sulfate ions, 3 g / L or more of Zn ions and 0.10 g / L or more of polyethylene particles.
  • the zinc-based plated steel sheet is a generic term for steel sheets obtained by plating zinc on a steel sheet by various manufacturing methods such as a hot dipping method, an electroplating method, a vapor deposition plating method, and a thermal spraying method. Call it. Moreover, both the hot-dip galvanized steel sheet (GI) which has not been alloyed and the alloyed hot-dip galvanized steel sheet (GA) which has been alloyed are included in the zinc-based plated steel sheet.
  • GI hot-dip galvanized steel sheet
  • GA alloyed hot-dip galvanized steel sheet
  • a hot dip galvanized layer As a zinc-based plating layer formed on the surface of the steel sheet, a hot dip galvanized layer, an alloyed hot dip galvanized layer, a hot dip zinc-aluminum alloy plated layer, a hot dip zinc-aluminum-magnesium alloy plated layer, an electrogalvanized layer, Examples thereof include, but are not limited to, an electro-zinc-nickel alloy plating layer, and all known zinc-based plating layers containing zinc are applicable.
  • the sliding resistance at the time of press molding is small, and the galvanized steel plate which has the outstanding press formability is obtained.
  • the friction coefficient between the galvanized steel sheet and the mold is significantly reduced. For this reason, it has stable and excellent press formability even for high-strength zinc-based plated steel sheets and relatively low-strength zinc-based plated steel sheets subjected to complicated forming.
  • Even in difficult molding such as deep drawing required for complex shapes such as back doors the sliding resistance is small at the risk of cracking during press molding, and the overhanging property is good.
  • it does not contain a fluororesin there is no fear of generation of harmful fumes during welding.
  • high strength assumes a tensile strength (TS) of 440 MPa or more
  • relatively low strength assumes a TS of less than 440 MPa
  • FIG. 1 is a schematic front view showing a friction coefficient measuring apparatus.
  • FIG. 2 is a schematic perspective view showing the bead shape and dimensions in FIG.
  • FIG. 3 is a schematic perspective view showing the bead shape and dimensions in FIG.
  • an oxide layer is provided on the surface of a zinc-based plated steel sheet comprising a steel sheet and a zinc-based plated layer formed on the steel sheet, the oxide layer has an average thickness of 20 nm or more, and the oxide layer during, characterized in that Zn and 30 mg / m 2 or more, the S 1.0 mg / m 2 or more, containing polyethylene particles having an average particle size of less 5.0 .mu.m 50 mg / m 2 or more 1000 mg / m 2 or less And
  • the lubrication mechanism of the oxide layer is not clear, it can be considered as follows. During sliding, a high surface pressure is generated between the mold and the zinc-based plated steel sheet, the lubricating oil is eliminated, and a portion that directly contacts the mold and the zinc-based plated layer is generated. Furthermore, shear stress is generated on the surface of the zinc-based plating layer due to the adhesion between the mold and the zinc-based plating. In such a case, the oxide containing Zn has an adhesion suppression force that suppresses direct contact between the mold and the steel plate. S is an element used as an extreme pressure additive.
  • S has an adhesion suppressing force that suppresses adhesion between the steel sheet and the mold by adsorbing to the surface of the zinc-based plated steel sheet or the mold even in a high surface pressure state where oil is excluded. Furthermore, by including polyethylene particles in the oxide layer, the polyethylene particles bear part of the sliding between the mold and the steel plate, and the friction coefficient is significantly reduced. Due to these synergistic effects, it is considered that excellent press formability can be obtained even under high surface pressure conditions during press forming of a high-strength steel plate and complex forming of a steel plate with relatively low strength.
  • the contents of Zn and S in the oxide layer are such that Zn is 30 mg / m 2 or more and S is 1.0 mg / m 2 or more.
  • Zn content of the oxide layer is less than 30 mg / m 2 and the S content is less than 1.0 mg / m 2 , it is difficult to obtain a sufficient sliding property improving effect, that is, a press formability improving effect.
  • the Zn content exceeds 1000 mg / m 2 and the S content exceeds 100 mg / m 2 , spot weldability and chemical conversion treatment, which are important in automobile production, may be deteriorated. Therefore, the Zn content is preferably 1000 mg / m 2 or less, and the S content is preferably 100 mg / m 2 or less.
  • the average thickness of the oxide layer is 20 nm or more. If it is less than 20 nm, sufficient press formability cannot be obtained. On the other hand, when it exceeds 200 nm, the reactivity of the surface is extremely lowered, and it may be difficult to form a chemical conversion treatment film. Therefore, the average thickness of the oxide layer is preferably 200 nm or less.
  • polyethylene particles are contained in the oxide layer as a solid lubricant.
  • Polyethylene is used for general purposes and is inexpensive.
  • the sufficient sliding characteristic improvement effect is acquired by containing a polyethylene particle in an oxide layer.
  • it may be thermally decomposed during welding to generate harmful gases such as HF and PFIB.
  • harmful gases such as HF and PFIB.
  • the present invention since only C and H are contained in the molecule, there is no concern that harmful fumes are generated or no harmful gas is generated during welding.
  • an organic resin is used in the present invention, a sufficient sliding characteristic improvement effect can be obtained as compared with inorganic solid lubricants such as molybdenum disulfide and boron nitride.
  • the average particle size is 5.0 ⁇ m or less.
  • the average particle diameter exceeds 5.0 ⁇ m, it is difficult to be taken into the oxide layer.
  • a preferable average particle diameter has a lower limit of 0.1 ⁇ m and an upper limit of 1.0 ⁇ m.
  • the total content of polyethylene (PE) is 50 mg / m 2 or more and 1000 mg / m 2 or less. If it is less than 50 mg / m 2 , a sufficient lubricating effect cannot be exhibited. On the other hand, in the case of exceeding 1000 mg / m 2 , spot weldability and chemical conversion processability are lowered. Preferably, it is from 50 mg / m 2 to 400 mg / m 2 .
  • the oxide layer formed on the surface of the galvanized steel sheet in the present invention can be analyzed by the following method.
  • the thickness of the oxide layer was measured using fluorescent X-rays, and the obtained oxygen intensity was converted to a silica film thickness based on the value of a silicon wafer on which a silicon oxide film with a known thickness was formed. Can be measured. Let the average value of the value measured from this be an average thickness of an oxide layer.
  • Zn, S, and O can be analyzed using an X-ray photoelectron spectrometer.
  • the average particle diameter of the polyethylene particles is obtained by measuring and averaging the particle diameters of any 20 polyethylene particles from the SEM observation image. It is possible to calculate the content by measuring the above and integrating the density into the total volume.
  • a sulfate group and a hydroxyl group exist in the oxide layer.
  • the presence or absence of a sulfate group and a hydroxyl group can be confirmed by the method of the Example mentioned later.
  • the oxide layer preferably further contains a P 0.2 mg / m 2 or more 10 mg / m 2 or less.
  • P a P 0.2 mg / m 2 or more 10 mg / m 2 or less.
  • P is considered to adhere to the surface in the form of a phosphoric acid compound, and the OH group present in the phosphoric acid compound improves the affinity with water and improves the wettability after degreasing. it is conceivable that. If the P content is less than 0.2 mg / m 2 , a sufficient degreasing effect may not be obtained. When it exceeds 10 mg / m 2, there is a concern that spot weldability, which is important in automobile production, is reduced.
  • the P content in the oxide layer was determined by analyzing a solution in which the oxide layer was dissolved with 2% by mass of ammonium dichromate + 14% by mass of aqueous ammonia using an ICP emission analyzer, and measuring the unit area. It can obtain
  • the manufacturing method of the zinc-plated steel plate of this invention is demonstrated.
  • the steel plate is subjected to a zinc-based plating treatment.
  • the method for performing the plating treatment is not particularly limited, and general methods such as hot dip galvanization and electrogalvanization can be employed.
  • the plating treatment conditions are not particularly limited, and preferable conditions may be adopted as appropriate.
  • an alloying treatment may be performed after plating.
  • the alloying method is not particularly limited, and a general method can be adopted.
  • polyethylene particles having an average thickness of 20 nm or more, Zn of 30 mg / m 2 or more, S of 1.0 mg / m 2 or more, and an average particle diameter of 5.0 ⁇ m or less
  • An oxide layer containing 50 mg / m 2 or more and 1000 mg / m 2 or less is formed.
  • the method for forming the oxide layer include a method in which a zinc-based plated steel sheet is brought into contact with an acidic solution containing sulfate ions, Zn ions, and polyethylene particles, and then washed with water. In addition, you may dry after water washing as needed.
  • the steel sheet is brought into contact with an acidic solution containing sulfate ions: 3 g / L or more, Zn ions: 3 g / L or more, and polyethylene particles: 0.10 g / L or more, and then washed with water.
  • an acidic solution containing sulfate ions: 3 g / L or more, Zn ions: 3 g / L or more, and polyethylene particles: 0.10 g / L or more, and then washed with water.
  • the method for producing polyethylene particles is not particularly limited.
  • a polyethylene product having an average particle size of 5.0 ⁇ m or less can also be used.
  • the acidic solution preferably has a pH of 2-6. When the pH is less than 2, the zinc-based plating layer is so dissolved that the formation of the oxide layer may be suppressed.
  • the pH of the acidic solution is preferably 2 or more and 6 or less.
  • the temperature of the acidic solution is preferably 20 to 80 ° C.
  • the temperature is less than 20 ° C.
  • the oxide layer formation rate is slow.
  • the temperature exceeds 80 ° C. the amount of evaporation of the solution increases, management of the liquid concentration becomes difficult, leading to an increase in cost, which is not preferable.
  • the contact time with the acidic solution is preferably 1 second to 500 seconds. If it is less than 1 second, a film having a sufficient film thickness may not be obtained. If it exceeds 500 seconds, the processing time becomes longer and the production cost increases.
  • the acidic solution contains an oxidizing agent.
  • the oxidizing agent include nitrates such as nitric acid and sodium nitrate, hydrogen peroxide, potassium permanganate and the like.
  • the formation mechanism of the oxide layer containing Zn, S, and polyethylene particles is not clear, it can be considered as follows.
  • a steel sheet coated with a zinc-based plating layer is brought into contact with an acidic solution containing sulfate ions, Zn ions and polyethylene particles
  • the pH of the steel sheet surface rises on the steel sheet side due to the zinc dissolution reaction and hydrogen ion reduction.
  • Zn, O and S are precipitated as compounds.
  • polyethylene particles are present in the solution near the steel plate, the polyethylene particles are taken into the Zn, O, and S compounds. And it is thought that the said oxide layer forms.
  • the sulfate ion in the solution in contact with the steel sheet is 3 g / L or more, the Zn ion is 3 g / L or more, and the polyethylene particles are 0.10 g / L or more.
  • the sulfate ion and Zn ion is less than 3 g / L, the deposition rate is slow, and it may be difficult to form a sufficiently thick oxide layer.
  • the polyethylene particles are less than 0.10 g / L, the amount taken into the oxide layer may be reduced.
  • the sulfate ion is 170 g / L or more
  • the Zn ion is 120 g / L or more
  • the polyethylene particles are 100 g / L or more
  • sulfate ions are less than 170 g / L
  • Zn ions are less than 120 g / L
  • polyethylene particles are less than 100 g / L.
  • the method of bringing the acidic solution into contact with the steel sheet is not particularly limited, the method of bringing the steel sheet into contact with the acidic solution, the method of bringing the steel sheet into contact with the acidic solution, and the acidic solution on the steel sheet using a coating roll There is a method of applying the coating.
  • the oxide layer further contains P in a content of 0.2 mg / m 2 or more and 10 mg / m 2 or less
  • P ions are contained in an amount of 0.01 g / L or more.
  • the steel sheet is brought into contact with the contained solution.
  • the S-based compound among the compounds containing Zn, S, and O undergoes a substitution reaction with the P-based compound, and the P-based compound is contained in the oxide layer. Is contained. If the concentration of P ions contained in the solution to be contacted is too small, the substitution rate is lowered, and a sufficient effect may not be obtained.
  • the concentration of P ions is preferably 0.01 g / L or more.
  • the P ion is 100 g / L or more, no further increase in the deposition rate can be expected. Therefore, it is preferably less than 100 g / L in view of cost.
  • the solution containing P ions sodium phosphate, sodium pyrophosphate, sodium polyphosphate aqueous solution and the like can be used. If P ions are contained, the same effect is exhibited, and there is no particular designation of the drug to be used.
  • N, Pb, Na, Mn, Ba, Sr, Si, Zr, Al, Sn, Cu, Be, B, F, Ne, and the like are taken into the oxide layer due to impurities contained in the solution.
  • the effect of the present invention is not impaired.
  • a high-strength cold-rolled steel sheet (TS: 590 MPa) having a thickness of 1.2 mm was subjected to electrogalvanizing (EG), hot-dip galvanizing (GI), and alloying treatment (GA) after hot-dip galvanizing.
  • EG electrogalvanizing
  • GI hot-dip galvanizing
  • GA alloying treatment
  • the steel sheet was immersed in the acid solution adjusted to the conditions shown in Table 1 under the conditions shown in Table 1. Next, it was washed with water and dried. About some steel plates, the steel plates were further immersed in the sodium pyrophosphate decahydrate solution at the concentrations, temperatures, and immersion times shown in Table 1. Next, after sufficiently washing with water, it was dried and P was contained in the oxide layer in an amount of 0.2 mg / m 2 to 10 mg / m 2 .
  • the Zn content, S content, P content, polyethylene particle content, and average thickness of the oxide layer contained in the oxide layer on the surface of the high-strength cold-rolled steel sheet obtained above were measured. In addition, the presence or absence of hydroxyl groups and sulfate groups was confirmed. Further, as a method for evaluating press formability, a friction coefficient was measured to evaluate sliding characteristics. In addition, the Zn content, the S content, the P content, the polyethylene particle content, the average thickness of the oxide layer, the presence form of Zn, S, and O in the surface layer of the high-strength cold-rolled steel sheet
  • the evaluation method of press formability (sliding characteristics) is as follows.
  • a silicon wafer on which a silicon oxide film having a thickness of 96 nm, 54 nm, and 24 nm cleaved to an appropriate size is set on the sample stage together with these series of samples.
  • the intensity of K ⁇ rays can be calculated.
  • a calibration curve between the oxide layer thickness and the O—K ⁇ ray intensity was prepared, and the thickness of the oxide layer of the test material was calculated as the oxide layer thickness in terms of silicon oxide film. Let the average value of the value measured from this be an average thickness of an oxide layer.
  • composition analysis of oxide layer Using a 2% ammonium dichromate solution + 14% by weight aqueous ammonia solution, the oxide layer alone was dissolved, and the solution was quantified for Zn, S, and P using an ICP emission spectrometer. Analysis was performed. The measured value was converted into the content per unit area, and the value was defined as the content.
  • Presence form of Zn, S, O Presence / absence of hydroxyl group and sulfate group
  • the presence forms of Zn, S, and O were analyzed using an X-ray photoelectron spectrometer. Using an Al Ka monochromatic radiation source, narrow measurement of the spectrum corresponding to Zn LMM, S 2p was performed.
  • (2) Evaluation method of press formability (sliding characteristic) In order to evaluate press formability, the friction coefficient of each test material was measured 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 when this is pushed up, a pressing load N applied to the friction coefficient measurement sample 1 by the bead 6.
  • a first load cell 7 is attached to the slide table support 5.
  • a second load cell 8 for measuring a sliding resistance force F for moving the slide table 3 in the horizontal direction in a state where the pressing force is applied is attached to one end of the slide table 3.
  • cleaning oil Preton R352L for press made from Sugimura Chemical Industry Co., Ltd. was apply
  • FIG. 2 and 3 are schematic perspective views showing the shape and dimensions of the beads used.
  • the bead 6 slides with its lower surface pressed against the surface of the sample 1.
  • the shape of the bead 6 shown in FIG. 2 is 10 mm in width, 5 mm in the sliding direction length of the sample, the lower part at both ends in the sliding direction is formed by curved surfaces with a curvature of 1.0 mmR, and the bottom 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 3 mm.
  • 3 has a width of 10 mm, a length of 59 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 having a curvature of 4.5 mmR. It has a plane with a direction length of 50 mm.
  • (3) Degreasing evaluation method Degreasing properties of some steel plates were evaluated. Degreasing was evaluated by the water wetting rate after degreasing. The prepared test piece was coated with 2.0 g / m 2 of cleaning oil Preton R352L for press made by Sugimura Chemical Co., Ltd., and then an alkaline degreasing solution of FC-E6403 made by Nihon Parkerizing Co., Ltd. was used. The sample was degreased.
  • the deterioration of the alkaline degreasing liquid in the automobile production line was simulated by adding 10 g / L of pre-cleaning oil Preton R352L for press produced by Sugimura Chemical Co., Ltd. to the degreasing liquid.
  • the degreasing time was 60 seconds, and the temperature was 37 ° C.
  • the degreasing solution was stirred with a propeller having a diameter of 10 cm at a speed of 150 rpm.
  • Degreasing was evaluated by measuring the water wetting rate of the test piece 20 seconds after the completion of degreasing.
  • No. 8-15, 17-20, 22-35, 40-43, 47-53 are invention examples. Sufficient Zn, S, and polyethylene particles are contained in the oxide layer, and the press moldability is excellent.
  • the comparative example is inferior in press formability.
  • the 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.

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Abstract

高強度の亜鉛系めっき鋼板および複雑な成形を施される比較的強度の低い亜鉛系めっき鋼板に対して、安定的に優れたプレス成形性を有し、かつ溶接時に有害ヒュームが発生することのない亜鉛系めっき鋼板およびその製造方法を提供する。　亜鉛系めっき鋼板の表面に酸化物層を有し、酸化物層は、平均厚さが２０ｎｍ以上であり、酸化物層中には、Ｚｎを３０ｍｇ／ｍ２以上、Ｓを１．０ｍｇ／ｍ２以上、平均粒子径が５．０μｍ以下であるポリエチレン粒子を５０ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下含有する。

Description

亜鉛系めっき鋼板およびその製造方法
　本発明は、プレス成形時の摺動抵抗が小さく、優れたプレス成形性を有する亜鉛系めっき鋼板およびその製造方法に関する。
　亜鉛系めっき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る。通常、亜鉛系めっき鋼板は、プレス成形を施した後に使用に供される。しかし、亜鉛系めっき鋼板は、冷延鋼板に比べてプレス成形性が劣るという欠点を有する。これはプレス金型での亜鉛系めっき鋼板の摺動抵抗が冷延鋼板に比べて大きいことが原因である。すなわち、金型とビードでの摺動抵抗が大きい部分で、摺動抵抗が大きい亜鉛系めっき鋼板がプレス金型に流入しにくくなり、鋼板の破断が起こりやすい。
　そのため、亜鉛系めっき鋼板使用時のプレス成形性を向上させる方法として、高粘度の潤滑油を塗布する方法が広く用いられる。しかし、この方法では、潤滑油が高粘性であるため、塗装工程で脱脂不良による塗装欠陥が発生する。また、プレス時の油切れにより、プレス性能が不安定になる等の問題がある。このため、亜鉛系めっき鋼板自身のプレス成形性の改善が要求されている。
　上記の問題を解決する方法として、特許文献１には、亜鉛系めっき鋼板の表面に電解処理、浸漬処理、塗布酸化処理、または加熱処理を施すことにより、亜鉛を主体とする酸化膜を形成させてプレス加工性を向上させる技術が開示されている。
　特許文献２には、鋼板を溶融亜鉛めっき後、加熱処理により合金化し、さらに調質圧延を施した後にｐＨ緩衝作用を有する酸性溶液と接触させ、所定時間保持した後水洗することでめっき表層に酸化物層を形成させ、プレス成形性を向上させる技術が開示されている。
　特許文献３には、調質圧延後の溶融亜鉛めっき鋼板を、ｐＨ緩衝作用を有する酸性溶液と接触させ、鋼板表面に酸性溶液の液膜が形成された状態で所定時間保持した後水洗、乾燥し、めっき表面に酸化物層を形成したプレス成形性に優れる溶融亜鉛めっき鋼板が開示されている。
　特許文献４には、電気亜鉛めっき鋼板を、ｐＨ緩衝作用を有する酸性溶液もしくは酸性の電気亜鉛めっき浴と接触させ、その後に所定時間保持した後水洗、乾燥し、めっき表面にＺｎ系酸化物を形成した、プレス成形性に優れる電気亜鉛めっき鋼板が開示されている。
　特許文献５には、亜鉛系めっき鋼板を酸性溶液に接触させ、所定時間保持し、水洗・乾燥を行うことにより表面に酸化物層及び／又は水酸化物層を形成する亜鉛系めっき鋼板の製造方法において、酸性溶液中に酸化物コロイドを含有させることにより、優れたプレス成形性を得る技術が開示されている。
　また、本出願人らは亜鉛系めっき鋼板をフッ素樹脂を含む酸性溶液に接触させ、所定時間保持し、水洗・乾燥を行うことにより、表面に、フッ素樹脂を含有する酸化物層及び／又は水酸化物層を形成し従来よりも格段に優れたプレス成形性を得る技術を提案した（特許文献６）。
特開平２－１９０４８３号公報 特許第３８０７３４１号公報 特許第４３２９３８７号公報 特開２００５－２４８２６２号公報 特許第５３８６８４２号公報 特開２０１６－０９８３８０号公報
　上記特許文献１～５に記載の技術を適用した場合、通常の亜鉛系めっき鋼板と比較すると良好なプレス成形性を得ることができる。しかし、近年では自動車車体の軽量化の観点から高強度の亜鉛系めっき鋼板が広く用いられるようになり、従来以上のプレス成形性が求められるようになっている。
　また、比較的強度の低い亜鉛系めっき鋼板に対しても、より複雑な成形を可能とするため、更なるプレス成形性の向上が必要である。
　上記特許文献１～５に記載の技術を高強度の亜鉛系めっき鋼板に適用した場合には必ずしも十分な効果を得ることができず、比較的強度の低い亜鉛系めっき鋼板に対しても、複雑な成形を可能とするには十分ではなかった。
　特許文献６に記載の技術では、皮膜中にフッ素樹脂を含むため、場合によっては溶接時に有害ヒュームが発生する可能性があり、ヒューム対策を施す必要があった。
　本発明は、かかる事情に鑑みてなされたものであって、高強度の亜鉛系めっき鋼板および複雑な成形を施される比較的強度の低い亜鉛系めっき鋼板に対して、安定的に優れたプレス成形性を有し、かつ溶接時に有害ヒュームが発生することのない亜鉛系めっき鋼板およびその製造方法を提供することを目的とする。
　本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、亜鉛系めっき鋼板の表面に、平均厚さが２０ｎｍ以上であり、Ｚｎ、Ｓおよびポリエチレン粒子を含有する酸化物層を形成することで、上記課題を解決できることを見出した。
　本発明は、以上の知見に基づき完成されたものであり、その要旨は以下の通りである。
［１］亜鉛系めっき鋼板の表面に酸化物層を有し、前記酸化物層は、平均厚さが２０ｎｍ以上であり、前記酸化物層中には、Ｚｎを３０ｍｇ／ｍ２以上、Ｓを１．０ｍｇ／ｍ２以上、平均粒子径が５．０μｍ以下であるポリエチレン粒子を５０ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下含有する亜鉛系めっき鋼板。
［２］前記酸化物層には、硫酸基及び水酸基が存在する上記［１］に記載の亜鉛系めっき鋼板。
［３］前記酸化物層中に、さらに、Ｐを０．２ｍｇ／ｍ２以上１０ｍｇ／ｍ２以下含有する上記［１］または［２］に記載の亜鉛系めっき鋼板。
［４］前記亜鉛系めっき鋼板は、合金化溶融亜鉛めっき鋼板、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板のいずれかである上記［１］～［３］のいずれかに記載の亜鉛系めっき鋼板。
［５］上記［１］～［４］のいずれかに記載の亜鉛系めっき鋼板の製造方法であって、
亜鉛系めっき鋼板を、硫酸イオンを３ｇ／Ｌ以上、Ｚｎイオンを３ｇ／Ｌ以上およびポリエチレン粒子を０．１０ｇ／Ｌ以上含有する酸性溶液に接触させる亜鉛系めっき鋼板の製造方法。
［６］前記酸性溶液は、ｐＨが２～６であり、温度が２０℃～８０℃である上記［５］に記載の亜鉛系めっき鋼板の製造方法。
［７］前記酸性溶液は、酸化剤を含有する上記［５］または［６］に記載の亜鉛系めっき鋼板の製造方法。
[８]前記亜鉛系めっき鋼板と前記酸性溶液との接触時間は１秒以上５００秒以下である上記［５］～［７］のいずれかに記載の亜鉛系めっき鋼板の製造方法。
［９］酸性溶液に接触後、Ｐイオンを０．０１ｇ／Ｌ以上含有する溶液に亜鉛系めっき鋼板を接触させる上記［５］～［８］のいずれかに記載の亜鉛系めっき鋼板の製造方法。
　本発明において、亜鉛系めっき鋼板とは、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（ＧＩ）、合金化処理を施す合金化溶融亜鉛めっき鋼板（ＧＡ）のいずれも亜鉛系めっき鋼板に含まれる。また、鋼板の表面に形成される亜鉛系めっき層として、溶融亜鉛めっき層、合金化溶融亜鉛めっき層、溶融亜鉛－アルミニウム合金めっき層、溶融亜鉛－アルミニウム－マグネシウム合金めっき層、電気亜鉛めっき層、電気亜鉛－ニッケル合金めっき層などが例示されるが、これらに限定されるものではなく、亜鉛を含む公知の亜鉛系めっき層すべてが適用可能である。
　本発明によれば、プレス成形時の摺動抵抗が小さく、優れたプレス成形性を有する亜鉛系めっき鋼板が得られる。
亜鉛系めっき鋼板と金型等との摩擦係数が顕著に低下する。このため、高強度の亜鉛系めっき鋼板や、複雑な成形を施される比較的強度の低い亜鉛系めっき鋼板に対しても安定的に優れたプレス成形性を有することになる。バックドアなどの複雑形状化に必要とされる深絞り加工などの難成形時においても、プレス成形時の割れ危険部位での摺動抵抗が小さく張り出し性が良好である。
また、フッ素樹脂を含有しないため、溶接時にも有害ヒューム発生の懸念がない。
　なお、上記において、「高強度」とは引張強度（ＴＳ）が４４０ＭＰａ以上を想定しており、「比較的強度の低い」とはＴＳが４４０ＭＰａ未満を想定している。
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中のビード形状・寸法を示す概略斜視図である。 図３は、図１中のビード形状・寸法を示す概略斜視図である。
　以下、本発明の実施形態について説明する。
　本発明では、鋼板と鋼板上に形成された亜鉛系めっき層とを備える亜鉛系めっき鋼板の表面に酸化物層を有し、酸化物層は、平均厚さが２０ｎｍ以上であり、酸化物層中には、Ｚｎを３０ｍｇ／ｍ２以上、Ｓを１．０ｍｇ／ｍ２以上、平均粒子径が５．０μｍ以下であるポリエチレン粒子を５０ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下含有することを特徴とする。
　上記酸化物層の潤滑メカニズムについては明確ではないが、以下のように考えることができる。摺動時には、金型と亜鉛系めっき鋼板の間には高い面圧が生じ、潤滑油が排除され、金型と亜鉛系めっき層には直接的に接触する部分が生じる。さらに金型と亜鉛系めっきの凝着力から亜鉛系めっき層の表面にはせん断応力が生じる。このような場合において、Ｚｎを含む酸化物には、金型と鋼板の直接的な接触を抑制する凝着抑制力がある。また、Ｓは極圧添加剤として使用される元素である。Ｓには、油が排除されるような高面圧状態においても、亜鉛系めっき鋼板表面あるいは金型に吸着することで、鋼板と金型の凝着を抑制する凝着抑制力がある。さらに、酸化物層中にポリエチレン粒子を含むことにより、ポリエチレン粒子が金型と鋼板の間の摺動の一部を担い、摩擦係数は著しく低下する。これらの相乗効果により、高強度鋼板のプレス成形時の高面圧条件や比較的強度の低い鋼板の複雑成形時においても、優れたプレス成形性を有することが可能となると考えられる。
　酸化物層中のＺｎおよびＳの含有量は、Ｚｎが３０ｍｇ／ｍ２以上、Ｓが１．０ｍｇ／ｍ２以上である。酸化物層のＺｎ含有量が３０ｍｇ／ｍ２未満、Ｓ含有量が１．０ｍｇ／ｍ２未満では十分な摺動特性向上効果、すなわち、プレス成形性向上効果を得ることが難しい。一方、Ｚｎ含有量が１０００ｍｇ／ｍ２超え、Ｓ含有量が１００ｍｇ／ｍ２超えになると、自動車製造の際に重要となるスポット溶接性や化成処理性が低下する場合がある。そのため、Ｚｎ含有量は１０００ｍｇ／ｍ２以下、Ｓ含有量は１００ｍｇ／ｍ２以下が好ましい。
　酸化物層の平均厚さは、２０ｎｍ以上とする。２０ｎｍ未満では十分なプレス成形性が得られない。一方、２００ｎｍを超えると表面の反応性が極端に低下し、化成処理皮膜を形成するのが困難になる場合がある。よって、酸化物層の平均厚さは２００ｎｍ以下とするのが好ましい。
　本発明では、固体潤滑剤として、酸化物層中にポリエチレン粒子を含有する。ポリエチレンは汎用的に使用されコストが安い。また、酸化物層中にポリエチレン粒子を含有することで十分な摺動特性向上効果が得られる。また、フッ素樹脂を含む場合、溶接時に熱分解し、ＨＦやＰＦＩＢなどの有害なガスが発生する可能性がある。これに対して、本発明では、分子中にＣおよびＨしか含まないため、溶接時に有害ヒュームが発生する懸念や有害ガスが発生する懸念がない。また、本発明では有機樹脂を使用するため、二硫化モリブデンや窒化ホウ素のような無機固体潤滑剤に比べ十分な摺動特性向上効果が得られる。
　酸化物層中にポリエチレン粒子を効率よく含有させるためには、平均粒子径は５．０μｍ以下とする。平均粒子径が５．０μｍを超えると、酸化物層中に取り込まれ難くなる。また、酸化物層との密着性が劣る傾向がある。好ましい平均粒子径は、下限が０．１μｍであり、上限が１．０μｍである。
　ポリエチレン(ＰＥ)の含有量は、合計で５０ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下とする。５０ｍｇ／ｍ２未満では十分な潤滑効果を発揮できない。一方、１０００ｍｇ／ｍ２超えの場合には、スポット溶接性や化成処理性が低下する。好ましくは、５０ｍｇ／ｍ２～以上４００ｍｇ／ｍ２以下である。
　本発明で亜鉛系めっき鋼板の表面に形成させる酸化物層は下記の方法で分析することが可能である。
酸化物層中のＺｎ含有量、Ｓ含有量については、重クロム酸アンモニウム２質量％＋アンモニア水１４質量％溶液で、酸化物層を溶解した溶液を、ＩＣＰ発光分析装置を用いて分析することで定量することが可能である。
　酸化物層の厚さについては、蛍光Ｘ線を用いて測定し、得られた酸素強度を、厚さが既知である酸化シリコン皮膜を形成したシリコンウエハーの値を基準として、シリカ膜厚に換算し測定することができる。これから測定した値の平均値を酸化物層の平均厚さとする。
　Ｚｎ、Ｓ、Ｏの存在形態はＸ線光電子分光装置を用いて分析することが可能である。
　酸化物層中のポリエチレン粒子については、ＳＥＭ観察像から、任意の２０個のポリエチレン粒子の粒径を測定し平均することでポリエチレン粒子の平均粒子径を求め、一定面積にあるポリエチレン粒子の存在数を測定し全体積に密度を積算することで含有量を算出することが可能である。
　酸化物層中には、硫酸基及び水酸基が存在することが酸化物層の安定性の観点で好ましい。なお、硫酸基及び水酸基が存在の有無は、後述する実施例の方法にて確認することができる。
　さらに、本発明では、酸化物層中に、さらに、Ｐを０．２ｍｇ／ｍ２以上１０ｍｇ／ｍ２以下含有することが好ましい。酸化物層中にＰを含有することで、自動車製造における脱脂工程において、鋼板表面に付着した油を除去する脱脂性を向上させることができる。Ｐを酸化物層中に含有しない場合、脱脂液が劣化した場合や、鋼板の塗油量が極端に多い場合に、脱脂工程において、十分に油を除去することができず、水はじきを生じ、化成処理、塗装など後工程に悪影響を及ぼす可能性がある。これに対して、Ｐはリン酸化合物の形態で表面に付着していると考えられ、リン酸化合物に存在するＯＨ基が水との親和性を向上させ脱脂後の水濡れ性が向上するものと考えられる。Ｐ含有量が０．２ｍｇ／ｍ２未満では十分な脱脂性向上効果が得られない場合がある。１０ｍｇ／ｍ２超えになると、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。
　酸化物層中のＰ含有量は、重クロム酸アンモニウム２質量％＋アンモニア水１４質量％溶液で酸化物層を溶解した溶液を、ＩＣＰ発光分析装置を用いて分析し、測定した値を単位面積あたりの含有量に換算することで求めることができる。
　本発明の亜鉛系めっき鋼板の製造方法について説明する。
まず、鋼板に、亜鉛系めっき処理を施す。めっき処理を施す方法は特に限定されず、溶融亜鉛めっき、電気亜鉛めっき等の一般的な方法を採用可能である。また、めっきの処理条件は特に限定されず、適宜好ましい条件を採用すればよい。さらに、めっき後に、合金化処理を施してもよい。なお、合金化処理の方法は特に限定されず、一般的な方法を採用可能である。
　次に、亜鉛系めっき鋼板の表面に、平均厚さが２０ｎｍ以上であり、Ｚｎを３０ｍｇ／ｍ２以上、Ｓを１．０ｍｇ／ｍ２以上、平均粒子径が５．０μｍ以下であるポリエチレン粒子を５０ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下含有する酸化物層を形成する。
酸化物層を形成する方法としては、亜鉛系めっき鋼板を、硫酸イオン、Ｚｎイオン、ポリエチレン粒子を含有する酸性溶液に接触させ、その後水洗を行う方法が挙げられる。なお、必要に応じて、水洗後に乾燥を行ってもよい。具体的には、鋼板を、硫酸イオン：３ｇ／Ｌ以上、Ｚｎイオン：３ｇ／Ｌ以上およびポリエチレン粒子：０．１０ｇ／Ｌ以上含有する酸性溶液と接触させた後、水洗を行う。平均粒子径が５．０μｍ以下であるポリエチレン粒子を用いるにあたって、ポリエチレン粒子の製造方法は特に限定しない。平均粒子径が５．０μｍ以下のポリエチレン製品を用いることもできる。
酸性溶液はｐＨが２～６であることが好ましい。ｐＨが２未満では亜鉛系めっき層の溶解が激しく、酸化物層の生成が抑制される場合がある。一方、ｐＨが６超えの酸性溶液では溶液中のＺｎイオンが析出し、スラッジが発生してしまう場合があり、好ましくなく、酸化物の形成も十分ではない場合がある。よって、酸性溶液のｐＨは２以上６以下が好ましい。
　酸性溶液の温度は２０～８０℃が好ましい。温度が２０℃未満では酸化物層形成速度が遅い。一方、温度が８０℃を超えると溶液の蒸発量が増加し、液濃度の管理が困難になり、コスト増大に繋がるため好ましくない。
　酸性溶液との接触時間は１秒以上５００秒以下が好ましい。１秒未満では十分な膜厚の皮膜が得られない場合がある。５００秒を超えると処理時間が長時間化し、生産コストが増大する。
　酸性溶液には酸化剤を含有することが好ましい。酸化剤の例として、硝酸や硝酸ナトリウムなどの硝酸塩、過酸化水素、過マンガン酸カリウムなどが挙げられる。酸性溶液に酸化剤を含有することにより、酸化物層の形成が促進され、短時間での酸化物層の形成が可能となる。
　Ｚｎ、Ｓ、およびポリエチレン粒子を含有する酸化物層の形成メカニズムについては明確ではないが、次のように考えることができる。亜鉛系めっき層を被覆した鋼板を硫酸イオン、Ｚｎイオンおよびポリエチレン粒子を含有する酸性溶液に接触させると、鋼板側では亜鉛の溶解反応と水素イオンの還元による水素発生が生じ鋼板表面のｐＨが上昇する。このときｐＨが上昇した鋼板表面付近の溶液中に硫酸イオンとＺｎイオンが存在するとＺｎ、Ｏ、Ｓが化合物として沈殿析出する。また、同時に鋼板付近の溶液中にポリエチレン粒子が存在すると、Ｚｎ、Ｏ、Ｓの化合物にポリエチレン粒子が取り込まれる。そして、上記酸化物層が形成すると考えられる。
　上記形成メカニズムの観点から、鋼板を接触させる溶液中の硫酸イオンは３ｇ／Ｌ以上、Ｚｎイオンは３ｇ／Ｌ以上、ポリエチレン粒子は０．１０ｇ／Ｌ以上含有することが好ましい。硫酸イオンおよびＺｎイオンがそれぞれ３ｇ／Ｌ未満の場合、析出速度が遅く、十分な厚さの酸化物層形成が困難となる場合がある。ポリエチレン粒子が０．１０ｇ／Ｌ未満の場合、酸化物層に取り込まれる量が少なくなる可能性がある。一方、硫酸イオンが１７０ｇ／Ｌ以上、Ｚｎイオンが１２０ｇ／Ｌ以上、ポリエチレン粒子が１００ｇ／Ｌ以上となると、それ以上の析出速度の増加は期待できない。そのため、コストとの兼ね合いから、硫酸イオンは１７０ｇ／Ｌ未満、Ｚｎイオンは１２０ｇ／Ｌ未満、ポリエチレン粒子は１００ｇ／Ｌ未満であることが好ましい。
　上記酸性溶液を上記鋼板に接触させる方法は特に限定されず、鋼板を酸性溶液に浸漬させて接触させる方法、鋼板に酸性溶液をスプレーして接触させる方法、塗布ロールを用いて鋼板上に酸性溶液を塗布する方法等がある。
　酸性溶液に接触後、水洗を行う。なお、必要に応じて、その後、乾燥を行ってもよい。なお、水洗、乾燥の方法は特に限定されず、一般的な方法を採用可能である。
　さらに、酸化物層中にさらにＰを含有量０．２ｍｇ／ｍ２以上１０ｍｇ／ｍ２以下含有する場合は、水洗、必要に応じて乾燥を行った後に、Ｐイオンを０．０１ｇ／Ｌ以上含有する溶液に鋼板を接触させる。水洗、乾燥後、Ｐを含有する溶液に鋼板を接触させることで、Ｚｎ、Ｓ、Ｏを含有する化合物のうちのS系化合物がＰ系化合物と置換反応し、酸化物層中にＰ系化合物が含有される。接触させる溶液中に含まれるＰイオンの濃度が少なすぎると置換速度が低下し、十分な効果が得られない可能性があるため、Ｐイオンの濃度は０．０１ｇ／Ｌ以上が好ましい。一方、Ｐイオンが１００ｇ／Ｌ以上となると、それ以上の析出速度の増加は期待できないため、コストとの兼ね合いから１００ｇ／Ｌ未満であることが好ましい。Ｐイオンを含有する溶液としてはリン酸ナトリウム、ピロリン酸ナトリウム、ポリリン酸ナトリウム水溶液などが用いることができる。Ｐイオンを含有していれば、同様の効果を発現し、特段、使用する薬剤を指定するものでは無い。
　なお、溶液中に不純物が含まれることによりＮ、Ｐｂ、Ｎａ、Ｍｎ、Ｂａ、Ｓｒ、Ｓｉ、Ｚｒ、Ａｌ、Ｓｎ、Ｃｕ、Ｂｅ、Ｂ、Ｆ、Ｎｅなどが酸化物層中に取り込まれても、本発明の効果が損なわれるものではない。
　以下、本発明を実施例により説明する。なお、本発明は以下の実施例に限定されない。
　板厚１．２ｍｍの高強度冷延鋼板（ＴＳ：５９０ＭＰａ）に対して、電気亜鉛めっき(ＥＧ)、溶融亜鉛めっき(ＧＩ)および溶融亜鉛めっき後に合金化処理(ＧＡ)を施した。引き続き、表１に示す条件に調整した酸性溶液に鋼板を表１に示す条件で浸漬した。次に、水洗を行った後、乾燥した。一部の鋼板については、さらに、表１に示す濃度、温度、浸漬時間で、ピロリン酸ナトリウム１０水和物の溶液に鋼板を浸漬した。次に、十分水洗を行った後、乾燥させ、酸化物層中に、Ｐを０．２ｍｇ／ｍ２以上１０ｍｇ／ｍ２以下含有させた。
　上記により得られた高強度冷延鋼板に対して表面の酸化物層中に含まれるZn含有量、S含有量、Ｐ含有量、ポリエチレン粒子含有量、酸化物層の平均厚さを測定した。また、水酸基および硫酸基の存在の有無を確認した。また、プレス成形性を評価する手法として摩擦係数の測定を実施し摺動特性を評価した。なお、高強度冷延鋼板表層のZn含有量、S含有量、Ｐ含有量、ポリエチレン粒子含有量、酸化物層の平均厚さ、Ｚｎ、Ｓ、Ｏの存在形態の測定方法（水酸基および硫酸基の存在の有無確認）、プレス成形性（摺動特性）の評価方法は以下の通りである。
　（１）酸化物層の分析
　酸化物層の平均厚さの測定
　亜鉛系めっき鋼板に形成された酸化物層の厚みの測定には蛍光Ｘ線分析装置を使用した。測定時の管球の電圧および電流は３０ｋＶおよび１００ｍＡとし、分光結晶はＴＡＰに設定してＯ－Ｋα線を検出した。Ｏ－Ｋα線の測定に際しては、そのピーク位置に加えてバックグラウンド位置での強度も測定し、Ｏ－Ｋα線の正味の強度が算出できるようにした。なお、ピーク位置およびバックグラウンド位置での積分時間は、それぞれ２０秒とした。
　また、試料ステージには、これら一連の試料と一緒に、適当な大きさに劈開した膜厚９６ｎｍ、５４ｎｍ及び２４ｎｍの酸化シリコン皮膜を形成したシリコンウエハーをセットし、これらの酸化シリコン皮膜からもＯ－Ｋα線の強度を算出できるようにした。これらのデータを用いて酸化物層厚さとＯ－Ｋα線強度との検量線を作成し、供試材の酸化物層の厚さを酸化シリコン皮膜換算での酸化物層厚さとして算出した。これから測定した値の平均値を酸化物層の平均厚さとする。
　酸化物層の組成分析
　重クロム酸アンモニウム２％＋アンモニア水１４質量％溶液を用いて、酸化物層のみを溶解し、その溶液を、ＩＣＰ発光分析装置を用いて、Ｚｎ、Ｓ、Ｐの定量分析を実施した。
測定した値を単位面積あたりの含有量に換算し、その値を含有量とした。
　ポリエチレン粒子の含有量分析
　走査型電子顕微鏡を用いて、加速電圧５ｋＶ、作動距離８．５ｍｍ、倍率５０００倍でランダムに抽出した５視野を観察し、ポリエチレン粒子の平均粒子径、個数を求めた。観察視野中の単位面積当たりのポリエチレン粒子の合計体積を求め、密度と掛け合わせることで含有量を算出し、５視野の平均値を求めてポリエチレン粒子の含有量とした。
　Ｚｎ、Ｓ、Ｏの存在形態（水酸基および硫酸基の存在の有無）
　Ｘ線光電子分光装置を用いて、Ｚｎ、Ｓ、Ｏの存在形態について分析した。Ａｌ　Ｋａ　モノクロ線源を使用し、Ｚｎ　ＬＭＭ、　Ｓ　２ｐに相当するスペクトルのナロー測定を実施した。

　（２）プレス成形性（摺動特性）の評価方法　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。
　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への押付荷重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を測定するための第２ロードセル８が、スライドテーブル３の一方の端部に取付けられている。なお、潤滑油として、スギムラ化学工業（株）製のプレス用洗浄油プレトンＲ３５２Ｌを試料１の表面に塗布して試験を行った。
　図２、図３は使用したビードの形状・寸法を示す概略斜視図である。ビード６の下面が試料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５ｍｍ、摺動方向両端の下部は曲率１．０ｍｍＲ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に示すビード６の形状は幅１０ｍｍ、試料の摺動方向長さ５９ｍｍ、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５０ｍｍの平面を有する。
　摩擦係数測定試験は以下に示す２条件で行った。
［条件１］
　図２に示すビードを用い、押し付け荷重Ｎ：４００ｋｇｆ、試料の引き抜き速度（スライドテーブル３の水平移動速度）：１００ｃｍ／ｍｉｎとした。
［条件２］
　図３に示すビードを用い、押し付け荷重Ｎ：４００ｋｇｆ、試料の引き抜き速度（スライドテーブル３の水平移動速度）：２０ｃｍ／ｍｉｎとした。
　供試材とビードとの間の摩擦係数μは、式：μ＝Ｆ／Ｎで算出した。
（３）脱脂性の評価方法
　一部の鋼板については脱脂性の評価を行った。脱脂性の評価は、脱脂後の水濡れ率で評価を行った。作成した試験片に、スギムラ化学工業（株）製のプレス用洗浄油プレトンＲ３５２Ｌを片面２．０ｇ／ｍ２塗油したのち、日本パーカライジング（株）製のＦＣ－Ｅ６４０３のアルカリ脱脂液を用いてサンプルの脱脂を行った。脱脂液にスギムラ化学工業（株）製のプレス用洗浄油プレトンＲ３５２Ｌを１０ｇ／Ｌを予め添加することで自動車生産ラインにおけるアルカリ脱脂液の劣化をシミュレートした。ここで、脱脂時間は６０秒とし、温度は３７℃とした。脱脂時は脱脂液を直径１０ｃｍのプロペラを１５０ｒｐｍの速度で攪拌した。脱脂完了から２０秒後の試験片の水濡れ率を測定することで、脱脂性の評価を行った。
　以上より得られた結果を表２に示す。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
　表１、２より以下の事項がわかる。
　Ｎｏ．８～１５、１７～２０、２２～３５、４０～４３、４７～５３は発明例である。酸化物層に十分なＺｎ、Ｓ、ポリエチレン粒子が含まれ、プレス成形性に優れる。
　一方、比較例はプレス成形性に劣る。
　Ｎｏ．１２について詳細な酸化物層分析を行ったところ、Ｘ線光電子分光装置を用いて、分析した結果、Ｚｎ　ＬＭＭに相当するピークが９８７ｅＶ付近に観察され、Ｚｎは水酸化亜鉛の状態として存在していることが分かった。同様に、Ｓ　２ｐに相当するピークが１７１ｅＶ付近に観察され、Ｓは硫酸塩として存在していることが分かった。他の実施例についても、同様の手順で水酸化亜鉛、硫酸塩を含有するかどうかについて調査した。存在、及び含有が確認されたものについては○、確認されなかったものには×として、調査した結果を表２中に示した。本発明例は、Ｎｏ．１２と同様に、水酸化亜鉛、硫酸塩を含有していることがわかる。
　また、脱脂性の評価の結果から、皮膜中にＰを含有するＮｏ．５１～５３は、Ｐイオンを含有する液で処理していないＮｏ．１２に比べて良好な脱脂性を有していることがわかる。
　本発明の鋼板はプレス成形性に優れることから、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　押付荷重
Ｆ　摺動抵抗力

Claims (9)

  1. 　亜鉛系めっき鋼板の表面に酸化物層を有し、
    前記酸化物層は、平均厚さが２０ｎｍ以上であり、
    前記酸化物層中には、Ｚｎを３０ｍｇ／ｍ２以上、Ｓを１．０ｍｇ／ｍ２以上、平均粒子径が５．０μｍ以下であるポリエチレン粒子を５０ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下含有する亜鉛系めっき鋼板。
  2. 　前記酸化物層には、硫酸基及び水酸基が存在する請求項１に記載の亜鉛系めっき鋼板。
  3. 　前記酸化物層中に、さらに、Ｐを０．２ｍｇ／ｍ２以上１０ｍｇ／ｍ２以下含有する請求項１または２に記載の亜鉛系めっき鋼板。
  4. 　前記亜鉛系めっき鋼板は、合金化溶融亜鉛めっき鋼板、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板のいずれかである請求項１～３のいずれかに記載の亜鉛系めっき鋼板。
  5. 　請求項１～４のいずれかに記載の亜鉛系めっき鋼板の製造方法であって、
    亜鉛系めっき鋼板を、硫酸イオンを３ｇ／Ｌ以上、Ｚｎイオンを３ｇ／Ｌ以上およびポリエチレン粒子を０．１０ｇ／Ｌ以上含有する酸性溶液に接触させる亜鉛系めっき鋼板の製造方法。
  6. 　前記酸性溶液は、ｐＨが２～６であり、温度が２０℃～８０℃である請求項５に記載の亜鉛系めっき鋼板の製造方法。
  7. 　前記酸性溶液は、酸化剤を含有する請求項５または６に記載の亜鉛系めっき鋼板の製造方法。
  8. 　前記亜鉛系めっき鋼板と前記酸性溶液との接触時間は１秒以上５００秒以下である請求項５～７のいずれかに記載の亜鉛系めっき鋼板の製造方法。
  9. 　酸性溶液に接触後、Ｐイオンを０．０１ｇ／Ｌ以上含有する溶液に亜鉛系めっき鋼板を接触させる請求項５～８のいずれかに記載の亜鉛系めっき鋼板の製造方法。
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