200521264 九、發明說明： 【潑^明所屬泛^技冬好領域】 技術領域 本發明係有關於一種經無機有機複合處理之鍵鋅鋼板。 發明背景 以往’為了提昇用於汽車、家電、建材等之鐘鋅鋼板之耐腐 姓性或塗膜密著性，一般係進行鱗酸鹽處理或鉻酸鹽處理。特別 是於施行磷酸鹽處理後，藉鉻酸鹽進行密封處理之方法對於提昇 耐腐蝕性或塗料密著性有很大之效果，因此廣為實施。然而，進 年來’於環境問題高漲之背景下，傾向於開發不使用毒性大之鉻 酉欠鹽之表面處理技術，而有如下之技術。 該技術係提供一種於鍍辞系鋼板之表面具有第丨層之磷酸鋅 處理皮膜層，並於該第1層上具有第2層之有機系皮膜之磷酸辞複 合處理鋼板(參照例如日本專利公開公報2〇〇1_1〇5528號），而前述 磷酸辞處理皮膜係含有選自於鎳、錳及鎂中之至少丨種之附著量 〇·2〜2.5g/m2者，且前述有機系皮膜係以選自於乙烯系樹脂、環氧 系樹脂、胺基甲酸酯系樹脂及丙烯酸系樹脂中之至少以重之有機 樹脂為主成分者。 另外，有於鋼板表面依序形成鍍辞皮膜、〇.3g/m2以上之粦酸 鋅處理皮膜、〇·3〜2g/m2之有機被膜，碌酸鋅被膜含有鎮，且，石粦 酸辞處理皮膜中之鎂/鱗(質量比)為〇15以上並且鎂量為2〇mg/m2 以上之有機複合鍍鋅鋼板（參照例如日本專利公開公報 200M31763號）。 200521264 實施過如前述之處理之鍍鋅系鋼板，通常於加壓成形並實施 驗脫脂洗淨後直接使用或經塗裝後使用。因此，需要無塗裝之耐 腐蝕性及塗裝後之耐腐蝕性兩者。 然而，利用如前述之方法等所得到之磷酸辞複合處理鋼板及 有機複合鑛鋅鋼板中，填酸辞皮膜與有機皮膜間於腐贿境下之 結合不強，謂經塗裝狀態放置於濕潤率極高之環境中時，磷酸 鋅皮膜與有機皮膜間會產生I嫌，而有塗裝後之耐麟嫩不足之 情況發生。200521264 IX. Description of the invention: [The field of technology and technology in the field of technology] The present invention relates to a bond zinc steel plate treated by inorganic-organic composite treatment. BACKGROUND OF THE INVENTION In the past, in order to improve the corrosion resistance or coating adhesion of a bell zinc steel sheet used in automobiles, home appliances, and building materials, a scale treatment or a chromate treatment is generally performed. In particular, the method of sealing with chromate after performing phosphate treatment has a great effect on improving corrosion resistance or paint adhesion, and is therefore widely used. However, in recent years, in the context of rising environmental problems, the tendency has been to develop a surface treatment technology that does not use the toxic chromium sulphate and undersalt, and has the following technologies. This technology is to provide a phosphate-treated composite steel sheet having a zinc phosphate-treated film layer on the surface of a plated steel sheet and a second layer of an organic-based film on the first layer (see, for example, Japanese Patent Publication) Bulletin No. 2000-1105528), and the aforementioned phosphate-treated film contains at least one adhesion amount selected from the group consisting of nickel, manganese, and magnesium of 0.2 to 2.5 g / m2, and the aforementioned organic film The main component is at least a heavy organic resin selected from the group consisting of vinyl resin, epoxy resin, urethane resin, and acrylic resin. In addition, a plating film, a zinc gallate treatment film of 0.3 g / m2 or more, and an organic coating of 0.3 to 2 g / m2 are sequentially formed on the surface of the steel sheet. An organic composite galvanized steel sheet having a magnesium / scale (mass ratio) of 0.15 or more and a magnesium content of 20 mg / m2 or more in the treatment film (see, for example, Japanese Patent Laid-Open Publication No. 200M31763). 200521264 Galvanized steel sheets that have been treated as described above are usually used directly after pressure forming and after degreasing and cleaning, or after coating. Therefore, both the corrosion resistance without painting and the corrosion resistance after painting are required. However, in the phosphate compound treated steel plate and the organic composite mineral zinc steel plate obtained by the method described above, the bonding between the acid-filled film and the organic film is not strong under the condition of corruption, which means that the coating is placed in a wet state. In an environment with a very high rate, I may be generated between the zinc phosphate film and the organic film, and there is a case that the inliner resistance after coating is insufficient.
【考务明内I 發明概要 於别述現狀’本發明之目的在於提供一種於經過處理之皮 膜中不含有害之鉻酸鹽，且可得到優異之耐腐蝕性之經無機無機 才炅合處理之鑛_辞鋼板。 本發明人等針對於鍍辞且具有磷酸辞皮膜與有機皮膜之經 無機有機複合處理之鍍辞鋼板，檢討各種提昇磷酸鋅皮膜與有機 皮膜間於腐蝕環境下結合之方法後，發現磷酸辞皮膜之底層之鍍 鋅層之狀態有很大之影響，而完成本發明。 本發明之要旨係提供一種經無機有機複合處理之鑛鋅鋼 板’前述經無機有機複合處理之鍍鋅鋼板係於鋼板上具有含有 〇·〇ΐ〜1%之鎳之鍍辞層，並於該鍍鋅層上具有含有鎂之磷酸鋅皮 膜’且更於該磷酸鋅皮膜上具有有機皮膜層者。其中前述磷酸鋅 皮膜中之鎂/鱗(質量比)為0.1以上，且鎂量為20mg/m2。又，前述 有機皮膜層含有環氧樹脂及/或變性環氧樹脂，又，前述有機皮膜 200521264 層之附著量為0.3〜5g/m2。 本發明之經無機有機複合處理之鑛辞鋼板之鍍鋅層不需要 電鍍、熱浸鍍方法，但必須含有〇·〇1〜1%之鎳。亦可一併含有錄 以外之不純物元素，例如鐵、鈷、鉛、銦、銥、錫、鈦等。鍍鋅 層之附著量並沒有特別限定，然而要求更高之耐腐蝕性時，係以 20g/m2以上為佳。 I：實施方式3 較佳實施例之詳細說明 以下，詳細地說明本發明。 本發明之經無機有機複合處理之鍍鋅系鋼板，係將鍍鋅層中 包含之鎳限定在0.01〜1%，因為於該範圍外時耐腐钱性不佳。鎳 為〇·〇1〜1%之範圍中會得到良好之耐腐蝕性之理由並不非常明 確，然而可以推想其中-個理由為形成於如前述之狀態之電鍍層 ^之魏辞賴之性狀纽變，喊上層之錢細層之密著性 變的良好。又，另外—個理由，可想到是因為即使有顧辞皮膜 無被覆而使鍍辞層露出之部分存在，亦可藉含有預定之鎳，使電 艘層與上層之有機皮膜層之密著性變的良好。 *磷酸辞處理皮膜可由含有碟酸離子及鋅離子之習知公知之 从鋅處理細蛾。前鱗離仅供給源，卩要是含有鋅之化合 物即可’並沒有特別限定，例如可舉财辞、氧化鋅、碳酸辞、 。肖S夂鋅等。丨4磷麟仅供給源，只妓含有顧德合物即 L並沒有特別限定，例如可舉例有鱗酸、五氧化鱗、石粦酸二氫 t。又’亦可含有之仙於磷酸鋅處理劑之其他成分。前 ，酸鋅處理皮膜必須含德。又，最好更含有鎳ϋ、銅、 200521264 及鐵等早獨讀或該等元素複合者^此，可更提昇麟鋼板之 对腐雜，且’可提昇與魏理皮朗之密著性。 前述魏鋅處理皮膜之皮膜中之鎮/磷(皮膜中之鎮與鱗之質 量⑹係刪以上為佳。小於0」時，可能無法看到因添加而提昇 财腐雜之效果。前述磷酸辞處理皮膜之皮膜中之㈣係以 以上為佳。小獅mg/m2時，恐無法提昇耐腐姓性。 W述磷酸鋅處理皮膜，係以下限〇 3咖2、上限5咖2之皮膜 置形成者為佳。小於G.3g/m2時，耐腐紐可能不^，而超過5咖2 時，於實施強烈加工時，皮膜恐會剝離。 形成前述顧鋅處理皮臈之處理液，可使用以鱗酸離子、辞 離子為主成分’且於必要時亦添加鋅以外之金屬離子、項酸離 子、氟化物離子等市售之處理液。欲使魏鋅處理皮膜中含有鎮 時’係以使用於前述魏鋅處理液中添加有魏麟之浴為佳。 皮膜中之鎮i及躺#之比可藉咖镇之添加量控制。 藉前述_域_處雜鋅峨之彻_處财法，不管 使用反應型處理、塗布型處理中任—種方法都可形成雜辞處理 皮膜。反顧處理’例如可於轉峨進行·旨、洗滌、表面調 整後，使該鋼板與前述磷酸鋅處觀接觸，並進行洗滌、乾燥來 形成填酸鋅處理皮膜。鱗酸辞處理皮膜之皮膜量，例如可藉改變 處理時間或處理劑濃度來調整。 塗布型處理，除了可於錢鋅鋼板將對應必要之皮膜量之量之 $述破st鋅處理液藉U法塗布以外’更有藉浸潰法或喷霧法塗 布後，藉1¾漸縮_整成必要之塗布量之方法。將《嫌辞處理劑 塗布於鑛鋅鋼板後，藉使用乾燥爐等乾燥，形成填酸鋅處理皮膜。 200521264 本發明之經無機有機複合處理之It辞鋼板，係於前述鱗酸辞 處理皮膜上具有有機皮膜層者，藉此可更進一步改善耐腐蝕性。 有機皮膜層含有有機樹脂’且為了提昇耐腐钱性，可摻入各種防 鏽添加劑或交聯劑。又，亦可配合目的，摻入用以給予滑動性之 蝶成分或給予圖案性之顏料等。 由密著性之觀點來看，有機樹脂係以含有環氧樹脂及/或變 性環氧樹脂為佳。有機皮膜層之附著量係以〇·3〜5g/m2為佳，小於 下限時耐腐蝕性不足，而超過上限時不易熔接。 有機皮膜層可於藉塗裝、喷霧、電鍍等方法塗布後，進行烘 烤乾燥來形成。 本發明之峨酸鋅處理層’係以於兩面處理為佳，然而對於有 機皮膜層，可於至少一面，即於最要求無塗裝之耐腐蝕性之面進 行處理。 實施例 以下，藉實施例詳細地說明本發明。 (鍍鋅鋼板) 於電鍍辞鋼板製造線中，使辞附著量(每一單面)g4〇g/m2， 製成於電鍍層中鎳含率不同之各種鍍鋅鋼板。 (磷酸辞處理） 於前述電騎處_紐行賴轉，物市f之碰膠體 系表面調整處理，並進行磷酸鋅處理。_鋅處理液係使用含有 Zn離子2.5g/l、Ni離子2·_、Mn離子2城、吻離子_、 離供/1者’藉儒如溫度45度及處理軸〜ι峨行洗祕 乾燥。 200521264 (有機皮膜處理) 使用前述經磷酸鋅處理之鍍鋅鋼板，進行有機皮膜處理。有 機皮膜處理係使用以水性樹脂為基底，並添加膠質氧化石夕固體且 使其成分重量比為16%所構成之塗料，而前述水性樹脂係於乙烯 變性環氧酯樹脂摻合嵌段異氰酸酯硬化劑、變性聚乙烯蠟、縮合 偶氮系之紅色顏料(固體成分重量比分別為1〇〇: 1〇: 5: 3)者，又， 藉輥塗機塗布，且烘烤到板溫度150°C，再以水冷卻。 (性能評價方法） 鍍鋅層中之鎳量：溶解電鍍層，並藉ICP分析定量。 磷酸鋅皮膜中鎂、磷量：使皮膜全部溶解，並藉ICP分析來 定量。又’填酸鋅皮膜量係由前述攝量假設H〇peite(磷鋅礦)之構 造後計算而算出。 有機皮膜量：藉螢光X線分析定量Si，並由組成比換算出皮 膜量。 無塗裝耐腐蝕性：以市售之洗淨油洗淨樣品後，進行U邊緣 考曲加工(樣品寬度7〇mm、BHF=lt〇n、力口工高度= 、邊緣 部衝壓R=5mm、邊緣部切割R=3mm、衝壓R=5mm、切割 5mm、加工速度= 25sPm)，切割其側面(切割面），並脫脂後，以 賽勝紛膠帶㈣端轉㈣，錢行CCT試驗*。祕15循環後 之紅鑛產生狀況。「〇」··小於1%，「△」·· 1〜1G%，「X」··超過10%。 塗裝岔著性：將樣品以市售之鹼脫脂液(ph=10.5、40°C、浸 ’貝1分鐘）進行汽車用化合處理（日本PAINT公司製撒服旦一 25〇〇MZL)後’進行汽車用陽離子電沉積（曰本PAINT公司製V20、 2〇μ、170且2〇分鐘之洪烤）。放置一天一夜後浸潰於贼溫水， 10 200521264 並於ίο天後取出 紛膠帶進彳ti· j造間隔lmm之健縫蝴贼，並以賽姆 離，「X」：剝離。」.沒有剝離，「△」：切割舰之周邊之制 。、rf後耐腐餘性：將樣品以市售之驗脫脂液(ph=la5、40 C ’又々1刀知)進行汽車用化合處理(日本p屋了公司製撒服旦一 500MZL)後’進行汽車用陽離子電沉積(曰本伙露公司製·、 2〇μ 170且2〇分鐘之烘烤）。製造通往地鐵之交叉切割瑕疵，並 驗*。測獅觀後之雜寬度。「〇」：小於lmm， 「△」：1〜2mm，「x」：超過2mm。 *CCT試驗條件：重複1循環之鹽水喷霧(5%NaCl，35)6小時 —乾燥(50°C 45%RH)3 小時―濕潤(50°C 95%RH) 14 小時—乾燥(5〇 °C45%RH)1小時。 於表1顯示以上之評價結果。 表1 鍍鋅之電鍍層中 之鎳百分比(％) 磷酸鋅皮膜 有機皮膜 皮膜量g/m2 性能評價 結果 皮膜量 g/m2 鎂/鱗質 量比 鎮量mg/m2 無塗 裝耐 腐蝕 性 塗 料 密 著 性 塗裝 後耐 腐蝕 性 實 施 例 1 _〜_ 0.02 1.0 0.17 23 0.7 〇 〇 〇 2 0.08 1.0 0.17 23 0.7 〇 〇 〇 3 0.25 1.0 ΟΛΊ^ 23 0.7 〇 〇 〇 4 0.77 1.0 0.17 23 0.7 〇 〇 〇 5 0.08 1.2 0.18 29 0.7 〇 〇 〇 6 0.08 1.4 0.18 34 0.7 〇 〇 〇 7 0.08 1.0 0.17 1 23 0.3 〇 〇 〇 8 0.08 1.0 0.17 23 1.2 〇 〇 〇— 9 0.08 1.0 0.17 23 2.0 〇 〇 〇 比 較 例 1 T T 檢測界限“ 1.0 0.17 23 0.7 〇 〇 X — 1.5 1.0 0.17 23 0.7 △ 〇 Δ 0.08 0.1 - 小於檢測界限u 0.7 X X X 4 0.08 1.0 0.17 23 -(無） X 〇 〇 *1 :小於0.005%、*2 :小於]mg/m2 200521264 與本發明之貫施例之良好特性者相比較下，超過本發明之範 圍以外之比較例之特性不佳。 產業上之可利用性 本發明之經無機有機複合處理之鍍辞鋼板，由於不使用鉻酸 鹽，可得到良好之耐腐錄，製造方法亦簡易，减本亦低，因 此，可適於使用在汽車、家電、建材等各種用途。[Summary of the Invention I. Summary of the Invention to the Present Situation 'The object of the present invention is to provide an inorganic-inorganic compound treatment that does not contain harmful chromate in the treated film and can obtain excellent corrosion resistance. Mine_Civil Plate. The present inventors have reviewed various methods for improving the combination of zinc phosphate film and organic film in a corrosive environment for inorganic-organic composite plated steel plates that are coated with a phosphate film and an organic film. The state of the zinc coating on the bottom layer has a great influence, and the present invention has been completed. The gist of the present invention is to provide an inorganic-organic composite-treated mineral zinc steel sheet. The foregoing inorganic-organic composite-treated zinc-plated steel sheet has a plating layer containing 0 · 〇ΐ ~ 1% of nickel on the steel sheet, and A zinc phosphate film containing magnesium on the galvanized layer and an organic film layer on the zinc phosphate film. The magnesium / scale (mass ratio) in the aforementioned zinc phosphate film was 0.1 or more, and the amount of magnesium was 20 mg / m2. The organic film layer contains an epoxy resin and / or a denatured epoxy resin, and an adhesion amount of the organic film 200521264 layer is 0.3 to 5 g / m2. The zinc-plated layer of the inorganic-organic composite treated steel sheet of the present invention does not require electroplating or hot-dip plating, but must contain 0.001 to 1% of nickel. It may also contain elements other than impurities such as iron, cobalt, lead, indium, iridium, tin, and titanium. The adhesion amount of the galvanized layer is not particularly limited, but when a higher corrosion resistance is required, it is preferably 20 g / m2 or more. I: Detailed description of the preferred embodiment of the third embodiment Hereinafter, the present invention will be described in detail. The inorganic-organic composite treatment of the galvanized steel sheet of the present invention limits the nickel contained in the galvanized layer to 0.01 to 1%, because corrosion resistance is not good when it is outside this range. The reason why nickel has a good corrosion resistance in the range of 0.001 to 1% is not very clear, but one reason can be inferred that it is the property of Wei Cilai, which is formed in the plating layer in the state described above. The change, shouting of the upper layer of money, the fine layer of adhesiveness becomes better. Also, for another reason, it is conceivable that even if there is a part where the plating layer is exposed even though there is no coating on the Guci film, the adhesion of the electric ship layer and the upper organic film layer can be made by containing a predetermined nickel. Becomes good. * Phosphate-treated membranes can be treated from zinc containing fine acid ions and zinc ions. The front scale is only a source of supply, and it is not particularly limited if it contains a zinc-containing compound, and examples thereof include financial statements, zinc oxide, carbonate, and the like. Xiao S 夂 Zinc et al. 4 Lin is only a source of supply, and only prostitutes contain Gu De compound, that is, L is not particularly limited. Examples include scaly acid, pentoxide, and dihydrogen tartrate. It may also contain other ingredients of zinc phosphate treatment agent. Before, zinc acid treatment film must contain German. Also, it is better to contain nickel rhenium, copper, 200521264, and iron alone or those elements ^ This can further improve the corrosion of Lin steel plate, and 'can improve the adhesion with Wei Lipi Lang . The town / phosphorus in the film of the aforementioned Wei-Zinc-treated film (the quality of the town and the scale in the film is better than the above. When it is less than 0 ", the effect of increasing wealth and impurities due to addition may not be seen. The aforementioned phosphate word The treatment of the film in the film is better than the above. At lion mg / m2, the corrosion resistance may not be improved. The zinc phosphate treatment film is a film with a lower limit of 0, 2 and an upper limit of 5 and 2 coffee. It is better to be formed. When it is less than G.3g / m2, the corrosion resistance may not be ^, and when it is more than 5 coffee, the film may be peeled off during the intense processing. Use a commercially available treatment solution containing scaly acid ions and ion ions as the main ingredients, and if necessary, metal ions other than zinc, acid ions, fluoride ions, and the like are added. If you want to make the Zinc treatment film contain the town time, It is better to use the bath with Wei Lin added to the aforementioned Wei-Zinc treatment liquid. The ratio of town i and lying # in the film can be controlled by the amount of coffee town. By the aforementioned _ 域 _ 处 杂 Zn 埃 之 彻 _ 处 财 法No matter which method is used for reaction type treatment or coating type treatment, it can form impurities. Treatment of the film. The retrospective treatment can be carried out, for example, after turning around, washing, and adjusting the surface. Then, the steel plate is brought into contact with the zinc phosphate, and washed and dried to form a zinc-filled zinc-treated film. The film amount of the film can be adjusted, for example, by changing the treatment time or the concentration of the treatment agent. The coating type treatment can be applied to the zinc zinc steel plate by applying the amount of the required coating amount to the zinc coating solution by the U method. In addition, after coating by dipping or spraying, it can be reduced by 1¾ to a necessary coating amount. After coating the suspicion treatment agent on the mineral zinc steel plate, it is dried by using a drying furnace to form acid filling. Zinc-treated film. 200521264 The inorganic-organic composite-treated It stainless steel sheet of the present invention is an organic film layer on the aforementioned scale acid-treated film, thereby further improving the corrosion resistance. The organic film layer contains an organic resin ' In addition, in order to improve the corrosion resistance, various anti-rust additives or cross-linking agents can be incorporated. In addition, it can also incorporate butterfly ingredients to give sliding properties or pigments to give pattern properties to suit the purpose. From the viewpoint of adhesion, the organic resin is preferably one containing epoxy resin and / or modified epoxy resin. The adhesion amount of the organic film layer is preferably 0.3 to 5 g / m2, and the resistance is less than the lower limit. Corrosiveness is insufficient, and it is not easy to weld when the upper limit is exceeded. The organic film layer can be formed by coating, spraying, electroplating, etc., and then baking and drying. The zinc ferric acid treatment layer of the present invention is treated on both sides. Preferably, however, the organic film layer can be treated on at least one side, that is, the side where corrosion resistance without coating is most required. EXAMPLES The present invention will be described in detail below with reference to examples. (Galvanized steel sheet) In electroplating In the steel sheet manufacturing line, the adhesion amount (each side) of g40 g / m2 is made of various galvanized steel sheets with different nickel content in the plating layer. (Phosphoric acid treatment) At the aforementioned electric riding place_New According to the change, the surface of the glue system of the material market f is adjusted and treated with zinc phosphate. _Zinc treatment liquid system contains 2.5g / l of Zn ions, Ni ions 2 · _, Mn ions 2 cities, kiss ions _, off donors / 1 persons' borrowing Ruru temperature 45 degrees and processing axis ~ ιE line washing secrets dry. 200521264 (Organic Coating Treatment) The aforementioned zinc phosphate-treated galvanized steel sheet was used for organic coating treatment. The organic film treatment is a coating composed of a water-based resin and a colloidal oxidized stone solid with a component weight ratio of 16%. The water-based resin is hardened by an ethylene-modified epoxy resin mixed with a block isocyanate. Agent, denatured polyethylene wax, condensed azo-based red pigment (solid content weight ratio is 100: 10: 5: 3 respectively), and also coated by a roll coater, and baked to a plate temperature of 150 ° C, and then cooled with water. (Performance evaluation method) The amount of nickel in the galvanized layer: the electroplated layer was dissolved and quantified by ICP analysis. Amounts of magnesium and phosphorus in zinc phosphate film: The film was completely dissolved and quantified by ICP analysis. The amount of zinc acid-filled film was calculated from the calculation after the construction of the above-mentioned assumed amount of Hopeite. Organic film amount: Si was quantified by fluorescent X-ray analysis, and the film amount was converted from the composition ratio. Corrosion resistance without coating: After washing the sample with a commercially available washing oil, perform U-edge test curve processing (sample width 70mm, BHF = lt〇n, force mouth height =, edge punch R = 5mm , Cutting edge edge R = 3mm, punching R = 5mm, cutting 5mm, processing speed = 25sPm), cut the side (cutting surface), and after degreasing, turn the end with Sai Shengfen tape, money line CCT test *. The status of red ore production after the 15th cycle. "〇" ... less than 1%, "△" ... 1 to 1G%, and "X" ... more than 10%. Coating breakability: After the sample is subjected to a compounding treatment for automobiles with a commercially available alkaline degreasing solution (ph = 10.5, 40 ° C, soaking for 1 minute) (Sapandan-2500MZL manufactured by Japan Paint Corporation) 'The cationic electrodeposition for automobiles was performed (V20, 20 μ, 170, and 20 minutes of flood roasting manufactured by Paint Corporation). After being left for one day and one night, it was immersed in warm thief water, 10 200521264, and taken out after a few days, the tape was taken into the ti · j to create a healthy seam butterfly with an interval of 1 mm, and separated by a sam. ". No peeling," △ ": The system around the cutting ship. Corrosion resistance after rf: After the sample is treated with a commercially available degreasing solution (ph = la5, 40 C 'and 1 knife), the compound is processed for automobiles (Sabudan-500MZL manufactured by Japan Piyale Co., Ltd.) 'Cation electrodeposition for automobiles (made by Benhoro, 20 μ 170 and 20 minutes baking). Create cross-cut flaws to the subway and check them out *. Measure the miscellaneous width after the lion view. "〇": less than 1 mm, "△": 1 to 2 mm, "x": more than 2 mm. * CCT test conditions: Repeat 1 cycle of saline spray (5% NaCl, 35) for 6 hours—dry (50 ° C 45% RH) for 3 hours—wet (50 ° C 95% RH) for 14 hours—dry (50%). ° C45% RH) for 1 hour. The above evaluation results are shown in Table 1. Table 1 Nickel percentage in galvanized plating layer (%) Zinc phosphate film Organic film film amount g / m2 Performance evaluation result Film amount g / m2 Magnesium / scale mass ratio ballast mg / m2 Unpainted corrosion-resistant coating dense Corrosion resistance after coating Example 1 _ ~ _ 0.02 1.0 0.17 23 0.7 〇〇〇〇 0.02 1.08 1.0 0.17 23 0.7 〇〇〇3 0.25 1.0 〇ΛΊ ^ 23 0.7 〇〇〇4 0.77 1.0 0.17 23 0.7 〇〇〇 5 0.08 1.2 0.18 29 0.7 〇〇〇〇6 0.08 1.4 0.18 34 0.7 〇〇〇07 0.08 1.0 0.17 1 23 0.3 〇〇〇0.08 1.0 0.17 23 1.2 〇〇-9 0.08 1.0 0.17 23 2.0 〇〇〇Comparative Example 1 TT detection limit "1.0 0.17 23 0.7 〇〇X — 1.5 1.0 0.17 23 0.7 △ 〇Δ 0.08 0.1-less than the detection limit u 0.7 XXX 4 0.08 1.0 0.17 23-(none) X 〇〇 * 1: less than 0.005%, * 2 : Less than] mg / m2 200521264 Compared with those with good characteristics of the conventional examples of the present invention, the characteristics of the comparative examples that are beyond the scope of the present invention are not good. Plated steel plate Since no chromate, corrosion can be obtained the good recording, also a simple method of manufacturing, this reduction is also low, and therefore, various applications can be adapted for use in automobiles, home appliances, and building materials.
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