JP7239008B2 - 亜鉛めっき鋼板 - Google Patents
亜鉛めっき鋼板 Download PDFInfo
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- JP7239008B2 JP7239008B2 JP2021549143A JP2021549143A JP7239008B2 JP 7239008 B2 JP7239008 B2 JP 7239008B2 JP 2021549143 A JP2021549143 A JP 2021549143A JP 2021549143 A JP2021549143 A JP 2021549143A JP 7239008 B2 JP7239008 B2 JP 7239008B2
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- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
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Description
[1]引張り強度が1180MPa以上の亜鉛めっき鋼板の表面に、0.5質量%のNaCl水溶液中に飽和濃度まで溶解した27℃の試験液中でのガルバニック電流が15μA/cm2以下となるような防錆添加剤を、30質量%~40質量%含有する有機樹脂皮膜を有する亜鉛めっき鋼板。
[2]前記0.5質量%のNaCl水溶液中に防錆添加剤が飽和濃度まで溶解した試験液の27℃でのpHが8.5~10.5である [1]に記載の亜鉛めっき鋼板。
[3]前記有機樹脂皮膜の膜厚が0.3~4μmである [1]または[2]に記載の亜鉛めっき鋼板。
[4]前記防錆添加剤が下記(a)から(e)のいずれか1種以上の不働態皮膜形成型の防錆添加剤である [1]から[3]のいずれかに記載の亜鉛めっき鋼板。
(b)アルミニウム、カルシウム、マグネシウム、シリコン、ジルコニウム化合物のいずれか1種以上を含むリン酸系防錆添加剤
(c)アルミニウムおよび/または亜鉛化合物を含むモリブデン酸系防錆添加剤
(d)マグネシウム化合物を含むタングステン酸系防錆添加剤
(e)カルシウムおよび/またはジルコニウム化合物を含むケイ酸塩
[5]前記有機樹脂皮膜が、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、エチレン樹脂、フェノール樹脂、ポリエステル樹脂の中から選ばれる1種類以上から成る[1]から[4]のいずれかに記載の亜鉛めっき鋼板。
有機樹脂としては、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、エチレン樹脂、フェノール樹脂、ポリエステル樹脂の中から選ばれる1種以上が好適に使用される。その理由は腐食の抑制効果がより大きく、加工時のめっき層の剥がれを防止する効果がより大きいためである。
「ガルバニック電流測定」
供試材を幅30mm×長さ100mmにせん断して試験片とした。一部の試験片の亜鉛めっきを濃度5質量%の塩酸で剥離し、ガルバニック電流測定用の下地鋼板試験片を作製した。亜鉛めっき鋼板の試験片1に対して、図1に示すように、直径24mmの円形測定面を露出させ、測定面以外はテープシールを用いて絶縁した。一方、下地鋼板の試験片1´に対しても、図1に示す試験片1の場合と同様に、直径24mmの円形測定面を露出させ、測定面以外はテープシールを用いて絶縁した。これらの試験片1と試験片1´とを、銅線4を用いて無抵抗電流計5を介して導通させてガルバニック対を形成し、下記の防錆添加剤を飽和溶解させた濃度0.5質量%の27℃のNaCl水溶液に、試験片1の測定面と試験片1´の測定面とを10mmの間隔をあけて向かい合わせにして浸漬させ、72時間放置して電流が十分に安定した時に流れていたガルバニック電流を評価した。その結果及び水溶液のpH測定結果を表1に示す。
オルトリン酸亜鉛(ホイバッハ製 ZMP)
リン酸ストロンチウム(ホイバッハ製 SRPP)
カルシウム交換シリカ(グレイス製 SHIELDEX-C303)
トリポリリン酸二水素アルミニウム(テイカ製 K-WHITE G750)
リン酸マグネシウム(キクチカラー製 MP-620)
亜リン酸カルシウム(キクチカラー製 CP-1300)
ケイ酸カルシウムジルコニウム(キクチカラー製 ZR-CS)
樹脂皮膜用の有機樹脂として下記A1~A4を用い、いずれかの有機樹脂と所定の防錆添加剤を含む処理液(比較例の一部では有機樹脂のみを含む処理液)を、鋼板表面に塗布方式(バーコート)、スプレー方式、浸漬方式(およびロール絞り)のいずれかで塗布した後、到達板温が140℃となるようにインダクションヒーターで加熱することで樹脂皮膜を形成した。
A2:アクリル樹脂(DIC(株)製、商品名:40-418EF)
A3:ウレタン樹脂(大日本塗料(株)製、商品名:VトップRCクリヤー)
A4:フッ素樹脂(旭硝子(株)製、商品名:ルミフロン(登録商標) LF552)
上記防錆添加剤を上記有機樹脂に添加混合して合金化溶融亜鉛めっき鋼板と冷延鋼板上に皮膜を形成させて供試材とした。供試材の有機樹脂の種別と膜厚および防錆添加剤の含有率を表2に示した。表2の皮膜が形成された発明例および比較例の高強度亜鉛めっき鋼板について、以下のようにして耐遅れ破壊性および塗装後耐食性を評価した。その結果を製造条件とともに表2に示す。
(1)耐遅れ破壊性の評価
発明例および比較例の鋼板を、それぞれ幅35mm×長さ100mmにせん断した後、せん断時の残留応力を除去するために幅が30mmとなるまで研削加工を施し、試験片を作製した。この試験片に対して、3点曲げ試験機を用いて90°曲げ加工を施し、図3に示すように、この曲げ試験片9を内側間隔が7mmとなるようにしてボルト7とナット8で拘束して試験片形状を固定し、耐遅れ破壊性評価用試験片を得た。このようにして作製した耐遅れ破壊性評価用試験片に対し、米国自動車技術会で定めたSAE J2334に規定された、乾燥・湿潤・塩水浸漬の工程からなる複合サイクル腐食試験を、最大40サイクルまで実施した。各サイクルの塩水浸漬の工程前に、目視により割れの発生の有無を調査し、割れ発生サイクルを測定した。また、本試験は、各鋼板3検体ずつ実施し、その平均値をもって評価を行った。評価はサイクル数から、以下の基準により評価した。なお、表2中の割れサイクル数40超とは、本実施例の結果では、割れが発生しなかったことを示す。〇または◎を合格とした。
〇:30サイクル以上、40サイクル以下
△:10サイクル以上、30サイクル未満
×:10サイクル未満
(2)塗装後耐食性の評価
発明例および比較例の鋼板を150mm×70mmにせん断して平板試験片とし、耐食性試験用試験片とした。この耐食性試験用試験片に、日本パーカライジング(株)製「パルボンド」(登録商標)を用い、標準条件(35℃、120秒)で浸漬による化成処理を施し、次いで、関西ペイント(株)製の電着塗料「GT-100」を用いた電着塗装と焼付処理を行った。電着塗装の塗膜厚は15μmとし、市販の電磁膜厚計を用いて膜厚の測定を行った。塗装後の試験片にカッターナイフを用いて素地に達するXカット(交差角60°~90°)を入れ、JISZ 2371で定められた塩水噴霧試験を840時間行い、試験後の試験片のクロスカットからの最大さび幅を計測し耐食性の評価を行った。
○:0.8<A≦0.95
△:0.95<A≦1.2
×:1.2<A
表1においてNo.1は、防錆添加剤を溶解させていない0.5質量%NaCl水溶液にガルバニック対を浸漬させた時に、ガルバニック対に流れる電流を示している。一方、No.2~8では防錆添加剤を飽和溶解させた0.5質量%のNaCl水溶液にガルバニック対を浸漬させた時に、ガルバニック対に流れる電流を示している。いずれもNo.1と比較してガルバニック電流が抑制されているが、水溶液のpHが8.5を上回る防錆添加剤(No.4~8)は、水溶液のpHが8.5を下回る防錆添加剤(No.2、3)よりもガルバニック電流を抑制していることがわかる。
1´ 亜鉛めっき鋼板から亜鉛めっきを塩酸で剥離した下地鋼板の試験片
2 シール
3 非シール部(測定面)
4 銅線
5 無抵抗電流計
6 防錆添加剤が飽和濃度まで溶解した0.5質量%NaCl水溶液
7 ボルト
8 ナット
9 曲げ試験片
Claims (4)
- 引張り強度が1180MPa以上の亜鉛めっき鋼板の表面に、0.5質量%のNaCl水溶液中に飽和濃度まで溶解した27℃の試験液中でのガルバニック電流が15μA/cm2以下となるような防錆添加剤を、30質量%~40質量%含有する有機樹脂皮膜を有し、前記防錆添加剤が下記(a)から(e)のいずれか1種以上の不働態皮膜形成型の防錆添加剤である亜鉛めっき鋼板。
(a)カルシウム交換シリカ
(b)アルミニウム、カルシウム、マグネシウム、シリコン、ジルコニウム化合物のいずれか1種以上を含むリン酸系防錆添加剤
(c)アルミニウムおよび/または亜鉛化合物を含むモリブデン酸系防錆添加剤
(d)マグネシウム化合物を含むタングステン酸系防錆添加剤
(e)カルシウムおよび/またはジルコニウム化合物を含むケイ酸塩 - 前記0.5質量%のNaCl水溶液中に防錆添加剤が飽和濃度まで溶解した試験液の27℃でのpHが8.5~10.5である請求項1に記載の亜鉛めっき鋼板。
- 前記有機樹脂皮膜の膜厚が0.3~4μmである請求項1または2に記載の亜鉛めっき鋼板。
- 前記有機樹脂皮膜が、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、エチレン樹脂、フェノール樹脂、ポリエステル樹脂の中から選ばれる1種類以上から成る請求項1から3のいずれかに記載の亜鉛めっき鋼板。
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