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JP3872621B2 - 自動車車体用亜鉛系メッキ鋼板 - Google Patents

自動車車体用亜鉛系メッキ鋼板 Download PDF

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Publication number
JP3872621B2
JP3872621B2 JP31500999A JP31500999A JP3872621B2 JP 3872621 B2 JP3872621 B2 JP 3872621B2 JP 31500999 A JP31500999 A JP 31500999A JP 31500999 A JP31500999 A JP 31500999A JP 3872621 B2 JP3872621 B2 JP 3872621B2
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Prior art keywords
zinc
coating
steel sheet
phosphate
film
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JP31500999A
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JP2001131762A (ja
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清和 石塚
英俊 新頭
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Nippon Steel Corp
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Nippon Steel Corp
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Priority to JP31500999A priority Critical patent/JP3872621B2/ja
Priority to TW089121719A priority patent/TW539767B/zh
Priority to US10/129,382 priority patent/US6623868B1/en
Priority to CA002387967A priority patent/CA2387967C/en
Priority to ES00970213T priority patent/ES2199871T3/es
Priority to EP00970213A priority patent/EP1234064B1/en
Priority to DE60003331T priority patent/DE60003331T2/de
Priority to KR1020027005742A priority patent/KR100652333B1/ko
Priority to PCT/JP2000/007636 priority patent/WO2001034874A1/en
Priority to AU79638/00A priority patent/AU767115B2/en
Publication of JP2001131762A publication Critical patent/JP2001131762A/ja
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • 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
    • Y10T428/12583—Component contains compound of adjacent 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

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  • Materials Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は主に自動車車体用途、更に詳しくは自動車外板用途に用いられる、耐食性、加工性に優れた亜鉛系メッキ鋼板に関するものである。
【０００２】
【従来の技術】
自動車車体用途の鋼板において、耐食性と加工性の要求がますます厳しくなってきている。特に耐食性については、ドアヘム部とよばれる鋼板と鋼板のあわせ部分における孔食が問題であり、この部分においては通常塗装が付着しないことから、鋼板裸での耐食性が要求されている。この耐食性の改善のため、２０ないし３０g/m2の薄目付けのZn-Ni系合金メッキを施し、更にその上層にクロメート皮膜、有機皮膜を形成した鋼板が広く使用されている。このような鋼板は、耐食性、加工性とも十分な性能を持つが、上層に有機皮膜の絶縁層を持つがゆえに、電着塗装時にムラが発生し易く、均一な塗装外観が得られ難い問題がある。それに加えて、高価なニッケルを使用することや、有害な６価クロムを含むといった問題もある。また、メッキ目付け量を増加した純亜鉛メッキ鋼板や、亜鉛鉄合金メッキ鋼板も使用されているが、一般にメッキの目付けを増加させれば耐食性の向上ともに加工性が悪化するため、両性能とも高度にバランスさせることは極めて困難である。
【０００３】
上記問題の解決のため、本発明者等は先に、亜鉛系メッキ鋼板またはリン酸亜鉛系化成皮膜を有する亜鉛系メッキ鋼板上にリン酸２水素Mgを含有する水溶液を塗布乾燥して皮膜を形成する方法を提案した。この方法では、良好な耐食性、加工性が得られるが、自動車外板用途を考慮した場合、必ずしも最適な皮膜構成ではない。すなわち、自動車外板用途の場合には、外面と内面で求められる要求特性が異なり、前述したような孔食に対するより高度な耐食性が要求されるのは主に内面側であり、外面側には耐食性よりも、塗装との適性や耐チッピング性が求められる。本発明者等が先に提案した方法は、耐孔食耐食性は十分なものであるが、塗装条件や使用環境によっては、耐チッピング性が必ずしも十分なものではなかった。
【０００４】
【発明が解決しようとする課題】
本発明では、上記欠点を解決し、耐食性と加工性を高度にバランスした、自動車外板用鋼板に最適の皮膜構成を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明の要旨は、自動車車体用に用いられる両面にメッキ皮膜を有する亜鉛系メッキ鋼板の自動車車体の外面に相当する面にはリン酸亜鉛皮膜を有し、内面に相当する面にはリン酸亜鉛皮膜と重リン酸 Mg 水溶液の塗布乾燥皮膜であるMgを含有するリン酸塩皮膜との複合リン酸塩皮膜を有し、複合リン酸塩皮膜が、 Mg を 2wt% 以上含有し、 0.5g/m 2 以上 2.5 g/m 2 以下の付着量であることを特徴とするものである。
【０００６】
【発明の実施の形態】
本発明に用いる亜鉛系メッキには特に限定がなく、純亜鉛メッキ、合金メッキのいずれについても使用でき、その良好な耐食性、加工性改善効果を享受できるが、製造コストの観点からは、電気亜鉛メッキ、溶融亜鉛メッキ、合金化溶融亜鉛メッキ等が好ましい。また単層メッキ、複層メッキいずれも使用できるし、Ni，Cu等のプレメッキ上に形成した亜鉛系メッキであっても構わない。
【０００７】
亜鉛系メッキ上に形成するリン酸亜鉛皮膜については特に限定はなく、Znイオン、リン酸イオン等を含有する市販の処理液によって皮膜を形成できる。リン酸亜鉛皮膜の付着量は通常、0.3〜2g/m2程度が好ましく、下限未満では耐食性、加工性が不足し、上限を超えると溶接性が悪化しやすい。リン酸亜鉛処理は通常、浸漬法またはスプレー法が用いられることから、表裏面の付着量に差を付けることは困難であり、また同付着量でいっこうに構わないが、例えば、表裏別々にスプレー処理を有する等の方法で表裏異付着量制御が可能であるならば、自動車外面に用いられる面の付着量は、内面に用いられる面の付着量よりも少な目に（例えば、0.1〜1.5g/m2）することが好ましい。外面に用いられる面であっても、付着量をゼロとすることは、溶接性が悪化したり、また表裏面の摺動性の差から、加工性が悪化する場合もあるため、最低でも0.1g/m2程度の付着量が必要である。
【０００８】
リン酸亜鉛皮膜中に、Ni,Mgを含有させることも、耐食性、加工性の観点から好ましく、この場合にはリン酸亜鉛処理液に前記金属イオンを含有させた浴で処理すればよい。
【０００９】
上記リン酸亜鉛皮膜上に、Mgを含有するリン酸塩水溶液を塗布乾燥することで、Mgを含有する複合リン酸塩被膜を形成でき、極めて良好な耐孔食耐食性を達成できるが、このようなMgを含有するリン酸塩水溶液の塗布乾燥皮膜は、高度の耐食性が要求される自動車内面に用いられる面のみに必須であり、外面には不要である。外面に前記皮膜を形成した場合、耐チッピング性が悪化することがある。内面相当面に形成する皮膜としては、リン酸亜鉛皮膜とMgを含有するリン酸塩水溶液の塗布乾燥皮膜との複合リン酸塩皮膜トータルとして、付着量は0.5g/m2以上、Mgは、2wt%以上必要であり、この場合に良好な耐食性が得られる。複合リン酸塩皮膜トータル付着量の上限は、加工性の観点から2.5g/m2以下が望ましい。 Mgを含有するリン酸塩水溶液としては、Mg(H2PO4) 2の組成を有する水溶液が好ましく、汎用性等を考慮すれば、市販の重リン酸Mg水溶液（例えば米山化学工業社製）が最も好ましい。これら水溶液をロールコーター等で片面（内面）にのみ塗布し、乾燥することで複合リン酸塩皮膜を形成する。
【００１０】
【実施例】
以下に本発明の実施例を示す。
試料調整（実施例１〜５および比較例１〜３）
母材として電気亜鉛メッキ鋼板（板厚0.7mm、目付量30g/m2/片面）を用い、表面調整（日本パーカライジング社製Pl-Zn)の後、日本パーカライジング社製のリン酸亜鉛処理浴（Znイオン0.7g/l、Niイオン2.0g/l、リン酸イオン6.5g/l、硝酸イオン6g/l、フッ化物0.2g/l）でスプレー処理を行った。りん酸亜鉛皮膜の付着量は、処理時間で調整して、表裏両面とも1g/m2となるようにした。りん酸亜鉛処理の後、重りん酸Mg水溶液を8%に希釈した液をロールコーターにより表裏別々に塗布し、到達板温度110℃となるように乾燥して放冷した。なお、実施例１〜５では、内板相当面にのみ塗布し、比較例２，３では、両方の面に塗布した。比較例１では、どちらの面にも塗布しなかった。重りん酸Mgの塗布乾燥皮膜の重量は、ロールコーターの回転数を制御することで調整した。重リン酸Mgを塗布した面については、複合リン酸塩皮膜の重量が表1に示す値になるように調整した。防錆油（パーカー興産製ノックスラスト530F60）を塗油して１日放置後以降の評価に供した。
【００１１】
試料調整（実施例６〜７）
前記例のリン酸亜鉛処理浴中に硝酸MgをMg濃度で30g/l添加することで、Mgを約4wt%含有するリン酸亜鉛皮膜を1.2g/m2両面に形成した。それ以外は、前記例と全く同様に処理し、内板相当面にのみ重リン酸Mg水溶液を塗布して、表１に示す付着量の複合リン酸亜鉛被膜を形成した。
【００１２】
評価方法
「複合リン酸亜鉛被膜の付着量」；反対面をテープシールした40mmφのサンプルをクロム酸溶液に浸漬して被膜を除去し、前後の付着量差を定量することで算出した。
「複合リン酸亜鉛被膜中のMg%」；前記のクロム酸溶液による溶解液を用いて、ICP分析により被膜中のMg量を定量し、Mg%を算出した。
「耐チッピング性」；70×150mmサンプルをアルカリ脱脂、自動車用化成処理、自動車用3コート塗装（カチオン電着塗装20μ、中塗り35μ、上塗り35μ）の順に行い、-20℃に冷却した状態で、5mm程度の径の石を合計500g分、3kgf/cm2の圧で90゜の角度で射出した。塗膜の浮き上がり部もカッターで除去した後、総剥離面積を画像解析法により算出した。（×；500mm2超、△；200〜500mm2、○；100〜200mm2、◎；100mm2未満）
【００１３】
「耐食性」；サンプルを市販の洗浄油で洗浄後、Ｕビード曲げ加工（サンプル幅70mm、ＢＨＦ＝１ton、加工高さ＝70mm、ビード部ポンチＲ＝5mm、ビード部ダイスＲ＝３mm、ポンチＲ＝5mm、ダイスＲ＝５ｍｍ、加工速度＝25spm）を行い、その側面（ダイス側）を切り出して、脱脂した後、端面と裏面をセロハンテープでシールし、ＣＣＴ試験*を行った。10サイクル後の赤錆発生状況を観察した。「◎」；０％、「○」；１％未満、「△」；１〜１０％、「×」；１０％超。
*CCT試験条件；塩水噴霧（5%NaCl,35）６時間→乾燥（50℃45%RH）３時間→湿潤（50℃95%RH）１４時間→乾燥（50℃45%RH）１時間、を１サイクルとした繰り返し。
【００１４】
「加工性」；市販洗浄油で洗浄の後、万能深絞り試験機にてＬＤＲ（限界絞り比）を測定した。プレス条件は、BHF=1ton、ポンチ径=40mmφ。なお、内板相当面をポンチ側とした。（×；ＬＤＲ値〜2.0、△；2.0〜2.2、○；2.2〜2.3、◎；2.3〜）
【００１５】
表１に、結果を示すが、本発明で規定する条件から外れるものは、何らかの性能が悪化した。
【００１６】
【表１】
Figure 0003872621
【００１７】
試料調整（実施例８〜10および比較例４）
先の実施例１〜５と同様の方法で、付着量0.5g/m2のリン酸亜鉛処理を施した。その後、重りん酸Mg水溶液を8%に希釈した液をロールコーターにより一方の面（内面）のみに塗布し、到達板温度110℃となるように乾燥して放冷した。塗布量を種々変更することで、実施例８〜10および比較例４のサンプルを造り分けた。防錆油（パーカー興産製ノックスラスト530F60）を塗油して１日放置後以降の評価に供した。
【００１８】
試料調整（実施例11〜12および比較例５）
リン酸亜鉛被膜の付着量が、0.2g/m2であること以外は、前記方法と同様に調整した。
評価方法は、前記例と同様である。
【００１９】
表２に、結果を示す。なお、外面側の耐チッピング性については、いずれも「◎」で良好であったことから、ここでは加工性と内面側の耐食性のみを示した。本発明で規定する条件から外れるものは、耐食性が悪化した。
【００２０】
【表２】
Figure 0003872621
【００２１】
【発明の効果】
本発明によって、自動車外板用途に求められる特性を高度にバランスした亜鉛系メッキ鋼板を得ることが可能になる。本発明の鋼板は諸特性に優れ、また、６価クロム等の有害物も使用せず、製造方法も簡易でコスト的にも優れ、自動車車体用鋼板として好適なものである。

Claims (2)

  1. 自動車車体用に用いられる両面にメッキ皮膜を有する亜鉛系メッキ鋼板の自動車車体の外面に相当する面にはリン酸亜鉛皮膜を有し、内面に相当する面にはリン酸亜鉛皮膜と重リン酸Mg水溶液の塗布乾燥皮膜であるMgを含有するリン酸塩皮膜との複合リン酸塩皮膜を有し、複合リン酸塩皮膜が、 Mg を 2wt% 以上含有し、 0.5g/m 2 以上 2.5 g/m 2 以下の付着量であることを特徴とする自動車車体用亜鉛系メッキ鋼板。
  2. リン酸亜鉛皮膜が、Ni,Mgを含むことを特徴とする請求項１に記載の自動車車体用亜鉛系メッキ鋼板。
JP31500999A 1999-11-05 1999-11-05 自動車車体用亜鉛系メッキ鋼板 Expired - Fee Related JP3872621B2 (ja)

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TW089121719A TW539767B (en) 1999-11-05 2000-10-17 Galvanized steel plate for use in vehicle body
CA002387967A CA2387967C (en) 1999-11-05 2000-10-31 Galvanized steel for use in vehicle body
ES00970213T ES2199871T3 (es) 1999-11-05 2000-10-31 Acero galvanizado de utilidad en carrocerias para vehiculos.
EP00970213A EP1234064B1 (en) 1999-11-05 2000-10-31 Galvanized steel for use in vehicle body
DE60003331T DE60003331T2 (de) 1999-11-05 2000-10-31 Galvanisiertes stahlblech zur verwendung in einem karosserieteil
US10/129,382 US6623868B1 (en) 1999-11-05 2000-10-31 Galvanized steel for use in vehicle body
KR1020027005742A KR100652333B1 (ko) 1999-11-05 2000-10-31 차체에 사용되는 아연도금강
PCT/JP2000/007636 WO2001034874A1 (en) 1999-11-05 2000-10-31 Galvanized steel for use in vehicle body
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JP4267213B2 (ja) * 2001-03-27 2009-05-27 新日本製鐵株式会社 耐食性および色調に優れたリン酸亜鉛処理亜鉛系メッキ鋼板
US8485544B2 (en) * 2009-04-21 2013-07-16 Great Dane Limited Partnership Method and apparatus for making galvanized upper coupler assembly
BR112014002026B1 (pt) 2011-07-29 2019-03-26 Nippon Steel & Sumitomo Metal Corporation Chapa de aço de alta resistência e chapa de aço galvanizado de alta resistência em fixabilidade de forma,e método de produção das mesmas.
CN103717773B (zh) 2011-07-29 2016-05-04 新日铁住金株式会社 弯曲性优异的高强度镀锌钢板及其制造方法
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TWI468534B (zh) 2012-02-08 2015-01-11 新日鐵住金股份有限公司 高強度冷軋鋼板及其製造方法
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