JP2001131762A - 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Info
- Publication number
- JP2001131762A JP2001131762A JP31500999A JP31500999A JP2001131762A JP 2001131762 A JP2001131762 A JP 2001131762A JP 31500999 A JP31500999 A JP 31500999A JP 31500999 A JP31500999 A JP 31500999A JP 2001131762 A JP2001131762 A JP 2001131762A
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- Prior art keywords
- steel sheet
- zinc phosphate
- film
- coated film
- galvanized steel
- Prior art date
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- 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
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- 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
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- 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
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- C23C22/08—Orthophosphates
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- 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
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- 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
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- 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
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- 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
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Abstract
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。 【解決手段】 本発明の要旨は、自動車車体用に用いら
れ、両面にメッキ皮膜を有する亜鉛系メッキ鋼板であっ
て、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Mgを含
有するリン酸塩皮膜との複合リン酸塩皮膜を有すること
を特徴とするものである。前記複合リン酸塩皮膜は、Mg
を2wt%以上含有し、0.5g/m2以上の付着量であることが
望ましい。
Description
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。
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。
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。
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。
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
Mgを含有するリン酸塩皮膜との複合リン酸塩皮膜を有す
ることを特徴とするものである。前記複合リン酸塩皮膜
は、Mgを2wt%以上含有し、0.5g/m2以上の付着量である
ことが望ましい。
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。
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、0.1〜1.5
g/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。
Alの1種または2種以上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。
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(H2P
O4) 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。
/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。
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。
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、3kg
f/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)
浄後、Uビード曲げ加工(サンプル幅70mm、BHF=1
ton、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=5m
m、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、端面と裏面をセロテープ
(登録商標)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。
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〜)
条件から外れるものは、何らかの性能が悪化した。
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。
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。
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。
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 (4)
- 【請求項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Mgを含有するリン酸塩皮膜との複
合リン酸塩皮膜を有することを特徴とする自動車車体用
亜鉛系メッキ鋼板。 - 【請求項2】 複合リン酸塩皮膜が、Mgを2wt%以上含有
し、0.5g/m2以上の付着量であることを特徴とする請求
項1に記載の亜鉛系メッキ鋼板。 - 【請求項3】 Mgを含有するリン酸塩皮膜が重リン酸Mg
水溶液の塗布乾燥皮膜であることを特徴とする請求項1
または2に記載の亜鉛系メッキ鋼板。 - 【請求項4】 リン酸亜鉛皮膜が、Ni,Mn,Mg,Co,Ca,Cu,
Alの1種または2種以上を含むことを特徴とする請求項
1または2または3に記載の亜鉛系メッキ鋼板。
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31500999A JP3872621B2 (ja) | 1999-11-05 | 1999-11-05 | 自動車車体用亜鉛系メッキ鋼板 |
TW089121719A TW539767B (en) | 1999-11-05 | 2000-10-17 | Galvanized steel plate for use in vehicle body |
US10/129,382 US6623868B1 (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 |
AU79638/00A AU767115B2 (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 |
CA002387967A CA2387967C (en) | 1999-11-05 | 2000-10-31 | Galvanized steel for use in vehicle body |
PCT/JP2000/007636 WO2001034874A1 (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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31500999A JP3872621B2 (ja) | 1999-11-05 | 1999-11-05 | 自動車車体用亜鉛系メッキ鋼板 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2001131762A true JP2001131762A (ja) | 2001-05-15 |
JP3872621B2 JP3872621B2 (ja) | 2007-01-24 |
Family
ID=18060329
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31500999A Expired - Fee Related JP3872621B2 (ja) | 1999-11-05 | 1999-11-05 | 自動車車体用亜鉛系メッキ鋼板 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6623868B1 (ja) |
EP (1) | EP1234064B1 (ja) |
JP (1) | JP3872621B2 (ja) |
KR (1) | KR100652333B1 (ja) |
AU (1) | AU767115B2 (ja) |
CA (1) | CA2387967C (ja) |
DE (1) | DE60003331T2 (ja) |
ES (1) | ES2199871T3 (ja) |
TW (1) | TW539767B (ja) |
WO (1) | WO2001034874A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001131763A (ja) * | 1999-11-09 | 2001-05-15 | Nippon Steel Corp | 有機複合亜鉛系メッキ鋼板 |
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 |
KR101598307B1 (ko) | 2011-07-29 | 2016-02-26 | 신닛테츠스미킨 카부시키카이샤 | 내충격 특성이 우수한 고강도 강판 및 그 제조 방법, 고강도 아연 도금 강판 및 그 제조 방법 |
WO2013018741A1 (ja) | 2011-07-29 | 2013-02-07 | 新日鐵住金株式会社 | 形状凍結性に優れた高強度鋼板、高強度亜鉛めっき鋼板およびそれらの製造方法 |
RU2569615C2 (ru) | 2011-07-29 | 2015-11-27 | Ниппон Стил Энд Сумитомо Метал Корпорейшн | Высокопрочный гальванизированный стальной лист, имеющий превосходную изгибаемость, и способ его производства |
TWI468534B (zh) | 2012-02-08 | 2015-01-11 | Nippon Steel & Sumitomo Metal Corp | 高強度冷軋鋼板及其製造方法 |
MX2015001944A (es) | 2014-02-13 | 2015-11-16 | Wabash National Lp | Ensamble de acoplador superior galvanizado. |
US9834264B2 (en) | 2014-12-29 | 2017-12-05 | Wabash National, L.P. | Upper coupler assembly |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3828676A1 (de) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | Phosphatierverfahren |
EP0453374B1 (en) * | 1990-04-20 | 1995-05-24 | Sumitomo Metal Industries, Ltd. | Improved corrosion-resistant surface coated steel sheet |
DE4440300A1 (de) * | 1994-11-11 | 1996-05-15 | Metallgesellschaft Ag | Verfahren zum Aufbringen von Phosphatüberzügen |
DE19808755A1 (de) * | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Schichtgewichtsteuerung bei Bandphosphatierung |
-
1999
- 1999-11-05 JP JP31500999A patent/JP3872621B2/ja not_active Expired - Fee Related
-
2000
- 2000-10-17 TW TW089121719A patent/TW539767B/zh not_active IP Right Cessation
- 2000-10-31 AU AU79638/00A patent/AU767115B2/en not_active Expired
- 2000-10-31 WO PCT/JP2000/007636 patent/WO2001034874A1/en active IP Right Grant
- 2000-10-31 CA CA002387967A patent/CA2387967C/en not_active Expired - Lifetime
- 2000-10-31 ES ES00970213T patent/ES2199871T3/es not_active Expired - Lifetime
- 2000-10-31 KR KR1020027005742A patent/KR100652333B1/ko active IP Right Grant
- 2000-10-31 DE DE60003331T patent/DE60003331T2/de not_active Expired - Lifetime
- 2000-10-31 US US10/129,382 patent/US6623868B1/en not_active Expired - Lifetime
- 2000-10-31 EP EP00970213A patent/EP1234064B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
TW539767B (en) | 2003-07-01 |
CA2387967A1 (en) | 2001-05-17 |
AU7963800A (en) | 2001-06-06 |
US6623868B1 (en) | 2003-09-23 |
CA2387967C (en) | 2006-12-12 |
WO2001034874A1 (en) | 2001-05-17 |
KR100652333B1 (ko) | 2006-11-29 |
JP3872621B2 (ja) | 2007-01-24 |
DE60003331D1 (de) | 2003-07-17 |
EP1234064B1 (en) | 2003-06-11 |
AU767115B2 (en) | 2003-10-30 |
EP1234064A1 (en) | 2002-08-28 |
ES2199871T3 (es) | 2004-03-01 |
DE60003331T2 (de) | 2004-04-29 |
KR20020068529A (ko) | 2002-08-27 |
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