201040315 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種鋼板及其製法，特別是指—種於 表面鈍化處理之鋼板及其製法。 【先前技術】 商業用鍍鋅鋼板在塗裝前，通常會先進行純化處理 以提昇鋼板之抗蝕性及烤漆塗裝性。一般常用之非鉻型鈍 化處理是利用磷酸鹽對鋼板進行表面處理，而於鋼板表面 〇 形成一層磷酸鋅皮臈。惟，單道次的磷酸鹽處理後所形成 的磷酸鋅並無法完全披覆鍍鋅鋼板的表面，也就是鋼板表 面仍存有未受保護之區域，致使鋼板的抗蝕性不足。針對 此抗蝕性不足的問題，通常會透過六價鉻之後處理來解決 ，但因為六價鉻具致癌性且會對環境造成污染，目前已被 限制使用，因此，鍍鋅鋼板的鈍化處理仍有待繼續研發。 曰本專利第2004-143475號所提出之解決方案是於鱗酸 鹽皮膜上塗佈一種液態組成物，該液態組成物含有至少一 〇 種選自於銅化合物、鈦化合物或锆化合物之金屬化合物， 該液態組成物可更含有一種含有雙酚A、胺及甲醛之縮聚合 樹脂化合物。日本專利第2001_105528號是於磷酸鋅皮臈上 形成一有機皮膜，該有機皮膜是由至少一種有機樹脂所形 成，該有機樹脂是選自於環氧樹脂、胺基甲酸酯樹脂或丙 烯酸系樹脂。 但是，上述兩專利所製成之鋼板在實際使用一段時間 後，卻發現磷酸鋅皮膜與有機皮膜之間的接著性不佳而易 201040315 產生剝離’以及有機皮膜容.易在後續鋼板焊接過程中裂解 而造成鋼板表面變色，x 1於形㈣酸辞皮膜及有機皮 膜之處理液中同時含有無機及有機化合物，使製備過程中 產生的廢液不易被回收。 由上述說明可知，如能有效解決磷酸辞皮膜無法全面 性披覆於鋼板表面㈣題，應有助於提昇_鋼板的耐钮 性’再者，若可更進一步在環保考量下改良鑛鋅鋼板之純 化處理步驟，將更能符合業界之需求。 【發明内容】 因此，本發明之目的，即在提供一種具有良好耐蝕性 且符合環保要求之經表面處理之鋼板。 本發明之另一目的是提供一種上述經表面處理之鋼板 的製法。 於是’本發明經表面處理之鋼板包含—具有一含辞表 面之鋼板本體、一形成於該含鋅表面上且含有磷酸辞及鎂 化合物之第一保護膜以及一形成於該第一保護膜上且含有 氧化鉬或氧化釩之第二保護膜。 本發明之經表面處理之鋼板的製法包含：於一具有一 含辞表面之鋼板本體上形成一第一保護膜以及於該第—保 護膜上形成一第二保護膜，其中該第一保護膜含有磷酸鋅 及鎂化合物’以及該第二保護膜含有氧化鉬或氧化鈒。 本發明經表面處理之鋼板透過在含鋅表面上形成_層 保護膜’即’含有鱗酸鋅及錢化合物之第—保護膜及含有 氧化鉬或氧化釩之第二保護膜。二保護膜形成之機制推測 201040315 為：當該鋼板本體浸泡於第一處理液時，該鋼板本體的含 鋅表面會解離出Zn2 ’並伴隨著H+(由第一處理液中解離） 還原成氫氣，此還原反應亦會使H2P〇4-及hpo42—解離出 P〇43_，最後Zn2+及P〇43-將會產生以下沉積反應： 3Ζη2++2Ρ〇43_+4Η20—Ζη3(Ρ〇4)2 · 4H20 ’而Mg2+亦分別與ΡΟ?-及OH-形成Mg3(P〇4)2及 Mg(OH)2(即上述之鎂化合物）’並同時覆蓋於含辞表面上。 接著，將該已形成第一保護膜之鋼板本體浸泡於第二 ❹ 處理液（以下利用鉬酸鹽進行說明）中，鉬酸鹽在pH值大於 4時會以MoOf存在，而未被磷酸鋅保護膜覆蓋之含鋅表 面將與第二處理液接觸並溶解，所釋放出的電子會讓 Mo042_還原成Mo02，即如以下反應所示：201040315 VI. Description of the Invention: [Technical Field] The present invention relates to a steel sheet and a method for producing the same, and particularly to a steel sheet which is subjected to surface passivation treatment and a method for producing the same. [Prior Art] Commercial galvanized steel sheets are usually purified prior to coating to improve the corrosion resistance and paintability of the steel sheets. The commonly used non-chromium type passivation treatment is to use a phosphate to surface-treat the steel sheet, and to form a layer of zinc phosphate skin on the surface of the steel sheet. However, the zinc phosphate formed by the single-pass phosphate treatment does not completely cover the surface of the galvanized steel sheet, that is, the unprotected area remains on the surface of the steel sheet, resulting in insufficient corrosion resistance of the steel sheet. The problem of insufficient corrosion resistance is usually solved by post-treatment of hexavalent chromium, but since hexavalent chromium is carcinogenic and pollutes the environment, it has been restricted, so the passivation treatment of galvanized steel sheets is still Need to continue research and development. The solution proposed in Japanese Patent No. 2004-143475 is to coat a scallate film with a liquid composition containing at least one metal compound selected from the group consisting of a copper compound, a titanium compound or a zirconium compound. The liquid composition may further comprise a polycondensation resin compound containing bisphenol A, an amine and formaldehyde. Japanese Patent No. 2001_105528 is an organic film formed on zinc phosphate skin, the organic film being formed of at least one organic resin selected from the group consisting of epoxy resins, urethane resins or acrylic resins. . However, after the actual use of the steel sheets made by the above two patents, it is found that the adhesion between the zinc phosphate film and the organic film is not good, and the peeling of the 201040315 is easy to occur, and the organic film capacity is easy to be in the subsequent steel plate welding process. The surface of the steel plate is discolored by cracking, and the inorganic liquid and organic compound are contained in the treatment liquid of the (4) acid film and the organic film, so that the waste liquid generated in the preparation process is not easily recovered. It can be seen from the above description that if it can effectively solve the problem that the phosphoric acid film cannot be fully coated on the surface of the steel plate (4), it should help to improve the resistance of the steel plate. In addition, if the mineral zinc plate can be further improved under environmental considerations The purification process will be more in line with the needs of the industry. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a surface treated steel sheet having good corrosion resistance and environmental protection requirements. Another object of the present invention is to provide a method of producing the above surface treated steel sheet. Thus, the surface-treated steel sheet of the present invention comprises a steel sheet body having a surface containing a surface, a first protective film formed on the zinc-containing surface and containing a phosphoric acid and a magnesium compound, and a first protective film formed on the first protective film. And a second protective film containing molybdenum oxide or vanadium oxide. The surface-treated steel sheet of the present invention comprises: forming a first protective film on a steel sheet body having a surface containing a word and forming a second protective film on the first protective film, wherein the first protective film The zinc phosphate and magnesium compound are contained and the second protective film contains molybdenum oxide or cerium oxide. The surface-treated steel sheet of the present invention is formed by forming a protective film on the zinc-containing surface, i.e., a first protective film containing zinc silicate and a money compound, and a second protective film containing molybdenum oxide or vanadium oxide. The mechanism of formation of the second protective film is presumed to be 201040315: when the body of the steel plate is immersed in the first treatment liquid, the zinc-containing surface of the body of the steel plate dissociates Zn2' and is reduced to hydrogen by H+ (dissociated from the first treatment liquid). This reduction reaction also causes H2P〇4- and hpo42—dissociated from P〇43_, and finally Zn2+ and P〇43- will produce the following deposition reactions: 3Ζη2++2Ρ〇43_+4Η20—Ζη3(Ρ〇4)2 · 4H20 ' and Mg2+ also forms Mg3(P〇4)2 and Mg(OH)2 (i.e., the above-mentioned magnesium compound) with ΡΟ?- and OH-, respectively, and simultaneously cover the surface of the word. Next, the body of the steel sheet on which the first protective film has been formed is immersed in the second ruthenium treatment liquid (described below using molybdate), and the molybdate is present as MoOf at a pH of more than 4, and is not zinc phosphate. The zinc-containing surface covered by the protective film will be in contact with and dissolved in the second treatment liquid, and the released electrons will reduce Mo042_ to Mo02, as shown in the following reaction:
Mo042~+4H++2e'-^ Mo02+2H20 再者，該第二保護膜含有氧化翻或氧化饥，相較於習 知所用之有機化合物’氧化鉬或氧化釩與磷酸鋅一樣皆屬 無機化合物，性質上較為相近而不易發生剝離情形，因而 〇 可有效提昇鋼板的耐蝕性。此外，因為製備過程中的廢液 僅含有無機化合物’亦有利於廢液的後續回收。 【實施方式】 在本發明之經表面處理之鋼板中，該鋼板本體是採用 具有一含鋅表面之鋼板本體，例如鍍鋅鋼板或表面鐵有辞 合金之鋼板。於本發明之一具體例中，該鋼板本體為一鍵 鋅鋼板。 較佳地’以該第一保護膜的總重為100 wt%計算，該第 5 201040315 保護膜的鎂化合物含量為20 wt%以上；又更佳地鎂化 〇物的3里範圍為2.0 wt%〜3.0 wt%。 、 在本發明之製法中，該第一保護膜可運用已知步驟進 仃製備，例如將該鋼板本體浸泡於第一處理液中，或將第 一處理液塗佈於該鋼板本體之含辞表面上，接著再進行供 乾。在上述浸泡或塗佈步驟中，可選擇地升高處理溫度p 例如將處理溫度升高為45。〔，讀進沉積反應的進行。 較佳地，該第一保護膜是由一第一處理液所製成，該 第一處理液含㈣酸、—可溶於水之含辞化合物及一可溶 於水之含鎂化合物，該含辞化合物主要是用於提昇第一處 理液中之Zn2+濃度，例如但不限於氧化鋅、石肖酸辞等等， 該含鎂化合物可例如但不限於硝酸鎂等’其作用是減小磷 酸辞核點大小與提升核點密度，以增加第一保護膜之穩定 性’同時可提昇鋼板的耐蝕性。又更佳地，該第理液 可含有《納’魏納主要是提供餐根作為促進劑，以 加速含鋅表面之轉並提供Zn2+4 Znl以與麟酸根產 生磷酸鋅。 較佳地，該第一處理液的PH值範圍為mj。 較佳地’該第一保護膜厚度約為2〜5μηι。 較佳地，該第二保謹胺I山 咕 . 犋疋由一第二處理液所製成，該 第二處理液的pH值範圍為4〜8。 δ弟一保濩臈亦可依據上述 第一保護膜的製程進行，且於、*# 於β泡或塗佈過程中，可選擇 地升南第·一處理液的溫度，么η 例如於本發明之一具體例中， 使用含有鉬酸鹽之第二處理游吐 . 、 处理液時，處理溫度可為6〇〇C ;而 201040315 於本發明之另一具體例中，使用含有釩酸鹽之第二處理液 時’處理溫度可為80。(：。 較佳地，該第二處理液含有一可溶於水之鉬酸鹽或銳 酸鹽、酸及水。更佳地，該第二處理液更含有磷酸鈉，以 有效維持第二處理液中之填酸根濃度。 當該第二處理液含有一可溶於水之錮酸鹽、酸及水時 ，該可溶於水之鉬酸鹽可例如但不限於鉬酸鈉、鉬酸鉀等 等。該酸可例如但不限於磷酸、硝酸、硫酸等等。更佳地Mo042~+4H++2e'-^ Mo02+2H20 Furthermore, the second protective film contains oxidized or oxidized hunger. Compared with the conventional organic compound, molybdenum oxide or vanadium oxide is the same as zinc phosphate. The compound is similar in nature and is not easily peeled off, so that the corrosion resistance of the steel sheet can be effectively improved. In addition, since the waste liquid in the preparation process contains only the inorganic compound', it is also advantageous for the subsequent recovery of the waste liquid. [Embodiment] In the surface-treated steel sheet of the present invention, the steel sheet body is a steel sheet having a zinc-containing surface, such as a galvanized steel sheet or a surface iron alloy. In one embodiment of the invention, the steel sheet body is a one-button zinc steel sheet. Preferably, the fifth 201040315 protective film has a magnesium compound content of 20 wt% or more based on the total weight of the first protective film of 100 wt%; and more preferably, the magnesium oxide has a range of 2.0 wt. %~3.0 wt%. In the method of the present invention, the first protective film can be prepared by a known process, for example, immersing the steel plate body in the first treatment liquid, or applying the first treatment liquid to the steel plate body. On the surface, it is then dried. In the soaking or coating step described above, the treatment temperature p is optionally increased, for example, by raising the treatment temperature to 45. [, read into the deposition reaction. Preferably, the first protective film is made of a first treatment liquid, and the first treatment liquid contains (tetra) acid, a water-soluble compound and a water-soluble magnesium-containing compound. The rhodium-containing compound is mainly used to increase the concentration of Zn2+ in the first treatment liquid, such as, but not limited to, zinc oxide, diaphoric acid, etc., and the magnesium-containing compound may be, for example, but not limited to, magnesium nitrate, etc. The size of the core is increased and the density of the core is increased to increase the stability of the first protective film' while improving the corrosion resistance of the steel sheet. Still more preferably, the first fluent may contain "na" Weiner primarily providing a meal root as a promoter to accelerate the conversion of the zinc-containing surface and provide Zn2+4 Znl to produce zinc phosphate with linonic acid. Preferably, the pH of the first treatment liquid ranges from mj. Preferably, the first protective film has a thickness of about 2 to 5 μm. Preferably, the second pharmaceutically acceptable amine I is prepared from a second treatment liquid having a pH in the range of 4 to 8. δ弟一保濩臈 can also be carried out according to the above-mentioned first protective film process, and in the *# in the β bubble or coating process, optionally the temperature of the first treatment liquid, η, for example, In a specific example of the invention, when the second treatment containing molybdate is used, the treatment temperature may be 6 〇〇C; and in 201040315, in another embodiment of the invention, the use of vanadate is used. The second treatment liquid may have a treatment temperature of 80. Preferably, the second treatment liquid contains a water-soluble molybdate or a sharp acid salt, an acid and water. More preferably, the second treatment liquid further contains sodium phosphate to effectively maintain the second The acid salt concentration in the treatment liquid. When the second treatment liquid contains a water-soluble ceric acid salt, an acid and water, the water-soluble molybdate may be, for example but not limited to, sodium molybdate, molybdic acid. Potassium, etc. The acid can be, for example but not limited to, phosphoric acid, nitric acid, sulfuric acid, etc. More preferably
’以該第二處理液之總重為⑽wt%計算，該第二處理液含 有0.1〜2.0 wt%之翻酸鹽。 當該第二處理液含有一可溶於水之鈒酸鹽、酸及水時 ，該可溶於水之㈣鹽可例如但不限純酸納、鈒酸卸等 等、。該酸可例如但不限於磷酸、姐、硫酸等等。更佳地 ，以該第二處理液之總重為_ wt%計算，該第二處理液含 有1.0〜6.0 wt%之鈒酸鹽。 較佳地’該第二保護膜的厚度為nm等級。 運用本發明製法所製得 我侍之經表面處理之鋼板透過在含 鋅表面披覆兼具抗蝕性、_ 著性及抗南溫變色的二層保續 膜’使得鋼板的壽命得以征旦 ^° 材等用途。 "Μ延長’並相於汽車、家電、建 一步說明，但應瞭解的 而不應被解釋為本發明 本發明將就以下實施例來作進 是，該實施例僅為例示說明之用， 實施之限制。 <實施例> 7 201040315 [製備例1〜7]第一及第二處理液的製備 製備例1 :將1.2g之氧化鋅、15g之硝酸鈉、1丨mi之磷酸（ 濃度為85°/。）、與1 〇〇〇g之水予以混合，並利用氫氧化 鈉水溶液將pH值調整至2.5，即製得第一處理液a。 除了另添加10g之Mg(N〇3)2 ·6Η2〇之外，其餘組成及 製法與第一處理液Α相同，最後製得第一處理液Β。 製備例2〜4 :分別將5g、10g及2〇g之Na2M〇〇4 .2Η2〇、 l〇g之Na3P04.l2H20與l〇〇〇g之水進行混合，再利 用85%之磷酸將調整至4_6,便分別製得第二處理液 Bl、B2 及 B3。 製備例5〜7 ··分別將15g、3〇g及6〇g之叫叫、1〇§之 ^Ρ〇4·12Η2〇與1〇〇〇g之水進行混合再利用85% 之磷酸將調整至4.6,便分別製得第二處理液B4、B5 及B6 〇 百先，取-鑛辞鋼板（由中國鋼鐵公司製造）作為試》 ’對此試片進行表面脫脂及去污，接著再浸泡至該第^ 理液B’並將處理溫度控制在㈣。待浸泡約工分心 後’以切子水沖洗⑻表面並加以 $ 面形成-第-保護膜。 ，並:第一保護膜之試片浸泡於第二處理液 子水沖洗試片表面並加以乾燥，便 :4 乂去離 …成—第二保護膜，同時製得實施例！之經表面處 201040315 理之鋼板試片。 [實施例2〜3] 除了將第二處理液B1分 刀別置換為B2及B3之外，其 餘製備過程皆與實施例1相间，县μ、 ^ 相门’最後分別製得實施例2及 3之經表面處理之鋼板試片。 【實施例4〜6] 除了將第二處理液m分別置換為Β4、β5αβ6以及 將第二保護膜之處理溫度控制為8〇〇c之外，其餘製備過 〇 ㈣與實施例1相同’最後分別製得實施例4〜6之經表面 處理之鋼板試片。 【比較例1] 除了未使用第二處理液來形成第二保護膜之外，其餘 製備過程皆與實施例1相同，最後分別製得比較例丨之經 表面處理之鋼板試片。 [比較例2] 除了將第一處理液B置換為第一處理液為a之外，其 ❹ 餘製備過程皆與比較例1相同’最後分別製得比較例2之 經表面處理之鋼板試片。 [測試] 將上述實施例1〜6及比較例1〜2所製得之經表面處理 之鋼板試片分別進行以下測試’所得結果分別如表1所示 9 1 元素含量分析·以電子微板分析儀（Electro Probe 2The second treatment liquid contained 0.1 to 2.0% by weight of the sulphate salt based on the total weight of the second treatment liquid of (10)% by weight. When the second treatment liquid contains a water-soluble bismuth salt, an acid and water, the water-soluble (tetra) salt may be, for example, but not limited to, sodium phthalate, ruthenium ruthenium or the like. The acid can be, for example but not limited to, phosphoric acid, sister, sulfuric acid, and the like. More preferably, the second treatment liquid contains 1.0 to 6.0 wt% of citrate based on the total weight of the second treatment liquid being _wt%. Preferably, the thickness of the second protective film is on the order of nm. The surface treated steel plate obtained by the method of the present invention can be used for the life of the steel plate by coating a zinc-containing surface with a two-layered retaining film which is resistant to corrosion, _ _ _ and anti-Southern temperature. ^° Materials and other uses. The present invention will be described with respect to the following embodiments, which are for illustrative purposes only, and should not be construed as the invention. Implementation restrictions. <Examples> 7 201040315 [Preparation Examples 1 to 7] Preparation of First and Second Treatment Liquids Preparation Example 1: 1.2 g of zinc oxide, 15 g of sodium nitrate, and 1 丨mi of phosphoric acid (concentration: 85°) /.), mixed with 1 〇〇〇g of water, and adjusted to a pH of 2.5 with an aqueous sodium hydroxide solution to obtain a first treatment liquid a. The composition and preparation method were the same as those of the first treatment liquid, except that 10 g of Mg(N〇3)2·6Η2〇 was additionally added, and finally the first treatment liquid was prepared. Preparation Examples 2 to 4: 5 g, 10 g, and 2 g of Na2M〇〇4.2.2Η2〇, l〇g of Na3P04.l2H20 and 1〇〇〇g of water were separately mixed, and then adjusted with 85% phosphoric acid. From 4 to 6, the second treatment liquids B1, B2 and B3 are separately produced. Preparation Examples 5 to 7 ··15g, 3〇g, and 6〇g, respectively, 1〇§^Ρ〇4·12Η2〇, mixed with 1〇〇〇g of water, and 85% phosphoric acid will be used. Adjusted to 4.6, the second treatment liquids B4, B5 and B6 were prepared separately, and the -minee steel plate (manufactured by China Iron and Steel Company) was used as a test. 'The test piece was surface degreased and decontaminated, and then Soak into the second liquid B' and control the treatment temperature at (4). After the immersion is about to be distracted, the surface of the (8) is rinsed with water and the surface is formed with a - protective film. And: the test piece of the first protective film is immersed in the surface of the second treatment liquid water rinsing test piece and dried, and then: 4 乂 离 成 第二 第二 - second protective film, and at the same time, the embodiment is prepared! The surface of the surface is 201040315. [Examples 2 to 3] Except that the second treatment liquid B1 was replaced by B2 and B3, the other preparation processes were the same as those in the first embodiment, and the county μ and ^ phase gates were finally prepared in Example 2 and 3 surface treated steel test pieces. [Examples 4 to 6] The preparation of the second treatment liquid m was the same as that of Example 1 except that the second treatment liquid m was replaced with Β4, β5αβ6, and the treatment temperature of the second protective film was controlled to 8 〇〇c. The surface-treated steel sheet test pieces of Examples 4 to 6 were separately prepared. [Comparative Example 1] The preparation process was the same as in Example 1 except that the second treatment liquid was not used to form the second protective film, and finally the surface-treated steel sheet test piece of Comparative Example was separately prepared. [Comparative Example 2] The remaining preparation process was the same as in Comparative Example 1 except that the first treatment liquid B was replaced with the first treatment liquid a, and finally the surface-treated steel sheet test piece of Comparative Example 2 was separately produced. . [Test] The surface-treated steel sheet test pieces obtained in the above Examples 1 to 6 and Comparative Examples 1 to 2 were subjected to the following tests, respectively, and the results obtained are shown in Table 1, respectively, and the content of the elements was analyzed by the electronic microplate. Analyzer (Electro Probe 2
Microanalyzer，簡稱為ΕΡΜΑ)進行鎂、钥或鈒元素 201040315 之含量的定量分析。 2. 抗飿性測试（鹽霧試驗& 4驗）.依據ASTM B117-03，調配 濃度5 %之鹽水，試η + t〜 大小控制為75mmx20mmxlmm 並將其端部及背部分 別以封邊膠及防鍍膠帶密封，接 著利用鹽水對著試片佳y_ 片進仃噴霧’噴霧時之試片傾角為 3〇度及噴霧時間為24 |吐 士生 1 小柃。在鹽霧試驗後，觀察白 鏽覆蓋面積，以白鏽#葚 ^ ^ 觸復盖面積百分比來評估耐蝕性。 若覆蓋面積大於5。/。則去丨中τ曰士 tMicroanalyzer (abbreviated as ΕΡΜΑ) performs quantitative analysis of the content of magnesium, key or strontium element 201040315. 2. Resistance test (salt spray test & 4 test). According to ASTM B117-03, mix 5 % salt water, try η + t~ size control is 75mmx20mmxlmm and seal the end and back respectively The glue and the anti-plating tape are sealed, and then the salt is applied to the test piece. The test piece is sprayed with a spray angle of 3 〇 and the spray time is 24 | 吐士生1小柃. After the salt spray test, the area covered by white rust was observed, and the corrosion resistance was evaluated by the percentage of the white rust #葚 ^ ^ contact area. If the coverage area is greater than 5. /. Then go to 丨中τ曰士 t
. ⑴列疋不具有耐蝕性，標註為「X J ;若覆蓋面積小於5〇/n目丨丨坐丨〜曰士上 /〇則判疋具有耐蝕性，標註為「 〇」。 3. 抗南溫變色測試：蔣叫y 办 將试片放入電阻式加熱爐中，並將 溫度加熱至450oC，烘姥$八热外1 又、烤5刀鐘。待試驗完畢後，觀 察試片表面是否變声。名：#y — A nI ,, 巴右6式片變色則判定不抗高溫， 標注為「X」；若試片未變色則判定具有抗高溫變色性 ，標註為「〇」。 4. 附著性測試（百格試驗）：依據ASTM D3359_〇2，以 百格試驗刀在試片表面交叉刻劃，接著以專用膠帶黏 貼於網狀刻痕處，撕開膠帶後以立體放大鏡觀察皮膜 的附著性。試驗後以皮膜脫落面積百分比來評估附著 性。若脫落面積為0%，判定為5B ;脫落面積小於5% ，判定為4B;脫落面積為5〜15%,判定為3B;脫落 面積為15〜35%，判定為2B，脫落面積為35〜65%， 判定為1B ;脫落面積大於65%，判定為〇B。 10 201040315 表1(1) Lennon does not have corrosion resistance and is marked as "X J ; if the coverage area is less than 5 〇 / n 丨丨 丨丨 丨 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 疋 疋 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 3. Anti-Southern temperature discoloration test: Jiang called y office Put the test piece into a resistance heating furnace, and heat the temperature to 450oC, bake $8 heat outside 1 and bake 5 knife. After the test is completed, observe whether the surface of the test piece has changed. Name: #y — A nI ,, Baro 6-type film is judged to be non-resistant to high temperature, marked as “X”; if the test piece is not discolored, it is judged to have high temperature discoloration resistance and is marked as “〇”. 4. Adhesion test (Hundred grid test): According to ASTM D3359_〇2, the surface of the test piece is cross-scored with a hundred-square test knife, then adhered to the mesh-like notch with a special tape, and the tape is removed after the tape is removed. Observe the adhesion of the film. Adhesion was evaluated as a percentage of the area of the film shedding after the test. If the falling area is 0%, it is judged as 5B; the falling area is less than 5%, it is judged as 4B; the falling area is 5~15%, it is judged as 3B; the falling area is 15~35%, it is judged as 2B, and the falling area is 35~ 65%, judged to be 1B; the shedding area is greater than 65%, and it is judged as 〇B. 10 201040315 Table 1
編號 細列1 侧列2 細列3 影fe例4 細列5 細列6 1 tbfei歹丨J2 第一 處理 液 鎂化合物 含量 (g/L) 1 1 1 1 1 1 1 0 第二 處理 液 鉬酸鹽或 釩酸鹽（ 含量g/L) 鉬酸鹽 (5) 鉬酸鹽 (10) 鉬酸鹽 (20) 飢酸鹽 (15) 釩酸鹽 (30) 釩酸鹽 (60) 無 無 鉬酸鹽或 鈒酸鹽含 量(wt%)a 0.49 0.97 1.90 1.47 2.87 2.52 0 0 第一 保護 膜 鎂化合物 含量 (wt%)b 2.01 2.10 2.03 2.12 2.04 2.11 2.16 0 第二 保護 膜 顧或叙含 量(wt%)b 翻 (0.82) 鉬 (0.63) 鉬 (0.98) 叙 (0.012) 鈒 (0.032) 飢 (0.031) 0 0 測試 結果 财钱性 〇 〇 〇 〇 〇 〇 x(20°/〇) x(70%) 抗高溫變 色性 〇 〇 〇 〇 〇 〇 〇 〇 附著性 5B 5B 5B 5B 5B 5B 5B 5B a.以第二處理液之總重為100 wt%計算。 b.透過ΕΡΜΑ進行定量分析。 [結果] 於表1之結果中，針對耐蝕性部分，可發現比較例1 、2之鋼板試片的耐蝕性不佳，而實施例1〜6之鋼板試片 皆具備良好的耐蝕性，可見實施例1〜6之鋼板試片在經過 第一及第二處理液的處理後，確實可有效提昇耐蝕性，也 同時證明本發明透過在含辞表面上形成第一保護膜及第二 保護膜，確實可有效提昇鋼板之耐蝕性。 11 201040315 /十對抗高溫變色性及附著性，可發現實施例η之鋼 板式片在經過第一及第二處理液的處理後，依然可呈備鱼 比較例1、2之鋼板試片_樣的抗高溫變色性及附著性，證 明本發明之經表面處理之鋼板可維持符合業界需求之抗高 溫變色性及附著性。 碎上所述，本發明經表面處理之鋼板透過在鋼板本體 :含鋅表面上形成含㈣酸辞及鎂化合物之第_保護膜及 3有氧化氧化鈒之第二保護冑，所製得之鋼板表面可 ，備良好的耐紐、抗高溫變色性及附著性，並讓鋼板的 壽7得以延長。本發明之製法所使用的第一及第二處理液 皆為無機溶液，使所產生的廢液種類較為單純，有利於後 續的回收處理。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 無 【主要元件符號說明】 無 12No. 1 side column 2 detail column 3 shadow fe case 4 detail column 5 detail column 6 1 tbfei 歹丨 J2 first treatment liquid magnesium compound content (g / L) 1 1 1 1 1 1 1 0 second treatment liquid molybdenum Acid or vanadate (content g/L) molybdate (5) molybdate (10) molybdate (20) oxalate (15) vanadate (30) vanadate (60) no Molybdate or citrate content (wt%) a 0.49 0.97 1.90 1.47 2.87 2.52 0 0 First protective film magnesium compound content (wt%) b 2.01 2.10 2.03 2.12 2.04 2.11 2.16 0 Second protective film Gu or Syria content ( Wt%)b Turn (0.82) Molybdenum (0.63) Molybdenum (0.98) Syria (0.012) 鈒 (0.032) Hunger (0.031) 0 0 Test result Treasury 〇〇〇〇〇〇x(20°/〇) x( 70%) High temperature discoloration 〇〇〇〇〇〇〇〇 adhesion 5B 5B 5B 5B 5B 5B 5B 5B a. Calculated based on the total weight of the second treatment liquid of 100 wt%. b. Quantitative analysis through ΕΡΜΑ. [Results] In the results of Table 1, it was found that the corrosion resistance of the steel plate test pieces of Comparative Examples 1 and 2 was poor for the corrosion resistance portion, and the steel plate test pieces of Examples 1 to 6 all had good corrosion resistance, and it was found that The steel sheet test pieces of Examples 1 to 6 can effectively improve the corrosion resistance after the treatment with the first and second treatment liquids, and also prove that the present invention forms the first protective film and the second protective film on the surface of the surface. It can effectively improve the corrosion resistance of the steel plate. 11 201040315 /10 against high temperature discoloration and adhesion, it can be found that the steel plate of the embodiment η can still be prepared for the fish sample of the comparative example 1 and 2 after the treatment of the first and second treatment liquids. The high temperature discoloration resistance and adhesion prove that the surface treated steel sheet of the present invention can maintain high temperature discoloration resistance and adhesion in accordance with industry requirements. According to the above, the surface-treated steel sheet of the present invention is formed by forming a first protective film containing a (4) acid word and a magnesium compound on the zinc-containing surface and a third protective layer containing oxidized cerium oxide. The surface of the steel plate can be prepared with good resistance to New Zealand, high temperature discoloration and adhesion, and the life of the steel plate can be extended. The first and second treatment liquids used in the production method of the present invention are all inorganic solutions, so that the type of waste liquid produced is relatively simple, which is advantageous for subsequent recovery treatment. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent. [Simple diagram description] None [Main component symbol description] None 12