201040314 六、發明說明： 【發明所屬之技術領域】 本發明疋有關於《— 今展ι # 巧荆、種1屬表面處理劑及其用途，特別 是指-種無鉻之金屬表面處理劑、使用此金屬表面處理劑 之金屬材料的表面處理方法。 【先前技術】 鍍鋼板（如鍛辞鋼板）具有良好的耐腐姓性、易於成型、 肖接及塗漆等優點’因而被廣泛應用於家電、電子產品、 〇 «及建㈣產業。不過，在使用-段時間後，料鋼板 之鑛鋅層於空氣中（尤其是高渥熱環境中）還是會被腐蚀而形 成白鑛，因此鋼板在鍍辞後需再進行純化處理。習知常使 祕酸鹽來進行鈍化處理，但隨著環保議題在各個產㈣ 逐漸被大幅重視’且歐盟於扇2年已將六價鉻列為有害物 質而不止使用，所以目前鋼板表面之處理已多數朝向無路 鈍化方式進行。 TW 506996揭示一種金屬表面處理劑，其含有㈧釩化 合物及（Β)含有至少-種選自於錯、欽、翻、鷄、鐘或飾之 金屬的金屬化合物。於此專利之實施财，除了上述的㈧ 及（Β)之外，尚添加蝕刻劑（HF、H2ZrF6、CH3C00h、 HzSiF6)且含釩化合物主要是使用+5價之釩化合物，使得部 分實施例在耐钱性測試之48小時後，發現彳1〇〜娜之白 鏽發生面積，顯見此專利之處理劑仍無法有效改善耐蝕性 。此外，此專利之處理劑於配製時需要較複雜之程序，且 處理劑中之溶解度及安定性尚有劣化之疑慮。 3 201040314 據上所述，如能改良金屬材料之表面處理劑，以改善 對金屬材料表面之耐蝕性、附著性、耐高溫性等等性質， 將有利於解決目前業界的問冑’同時可以擴展金屬材料的 應用。 【發明内容】 因此’本發明之㈣，即在提供一種無鉻、對金屬材 料表面具有良好之耐姓性、附著性及耐高溫性且易於製備 之金屬表面處理劑。 本發明之另-目的是提供一種利用上述金屬表面處理 劑之金屬材料之表面處理方法。 本發明之再一㈣是提供一制用丨述表面處理方法 之經表面處理之金屬材料。 於是，本發明金屬表面處理劑包含一有機釩化合物及 一含磷之無機酸，其中該有機釩化合物之釩離子的氧化數 非為+5。 本發明之金屬材料之表面處理方法包含將上述金屬表 面處理劑塗佈於一金屬材料表面的步驟。 本發明之經表面處理之金屬材料係包含一金屬材料本 體以及一形成於該金屬材料本體上之保護膜，該保護膜是 由上述金屬表面處理劑所製成。 金屬材料（如鍍鋅鋼板）之腐蝕過程是因為金屬表面滲入 腐餘因子（氧氣、水、氯離子等），進而誘使電化學之氧化還 原反應發生所致’也就是在陰極反應中，氧氣、水等得到 電子並產i OH ’使〇H濃度升高，而陽極反應則因金屬 201040314 == 。所以，在提_系鋼板的耐 時’可考慮財卩制陽極及陰極之氧化還原反應為重點201040314 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to "- 今展 ι # 巧 荆, species 1 surface treatment agent and its use, in particular, a chromium-free metal surface treatment agent, A surface treatment method of a metal material using this metal surface treatment agent. [Prior Art] Plated steel plates (such as forged steel plates) have good corrosion resistance, easy molding, splicing and painting. They are widely used in home appliances, electronic products, 〇 « and construction (four) industries. However, after a period of use, the ore zinc layer of the steel sheet is corroded to form white ore in the air (especially in a high heat environment), so the steel sheet needs to be further purified after plating. It is customary to use the acid salt for passivation treatment, but as environmental protection issues are gradually taken seriously in each production (four), and the EU has classified hexavalent chromium as a harmful substance in the fan for 2 years, it is not used. Processing has mostly been done towards passless passivation. TW 506996 discloses a metal surface treatment agent comprising (VIII) a vanadium compound and a metal compound containing at least one metal selected from the group consisting of a wrong, a chin, a turn, a chicken, a bell or a garnish. In addition to the above (8) and (Β), an etchant (HF, H2ZrF6, CH3C00h, HzSiF6) is added and the vanadium-containing compound is mainly a +5-valent vanadium compound, so that some embodiments are After 48 hours of the endurance test, it was found that the area of white rust occurred in 彳1〇~Na, and it is obvious that the treatment agent of this patent still cannot effectively improve the corrosion resistance. In addition, the treatment agent of this patent requires a complicated procedure in preparation, and the solubility and stability in the treatment agent are still degraded. 3 201040314 According to the above, if the surface treatment agent for metal materials can be improved to improve the corrosion resistance, adhesion, high temperature resistance and the like of the surface of the metal material, it will be helpful to solve the problem of the current industry' while expanding The application of metallic materials. SUMMARY OF THE INVENTION Therefore, (4) of the present invention provides a metal surface treatment agent which is chrome-free, has good resistance to the surname, adhesion and high temperature resistance on the surface of a metal material, and is easy to prepare. Another object of the present invention is to provide a surface treatment method for a metal material using the above metal surface treatment agent. Still another (4) of the present invention is to provide a surface-treated metal material using a surface treatment method. Accordingly, the metal surface treatment agent of the present invention comprises an organic vanadium compound and a phosphorus-containing inorganic acid, wherein the vanadium ion of the organic vanadium compound has an oxidation number of not +5. The surface treatment method of the metal material of the present invention comprises the step of applying the above metal surface treatment agent to the surface of a metal material. The surface-treated metal material of the present invention comprises a metal material body and a protective film formed on the metal material body, and the protective film is made of the above metal surface treatment agent. The corrosion process of metal materials (such as galvanized steel sheets) is caused by the infiltration of corrosion factors (oxygen, water, chloride ions, etc.) on the metal surface, which induces the electrochemical redox reaction to occur, that is, in the cathode reaction, oxygen , water, etc. get electrons and produce i OH 'to increase the concentration of 〇H, while the anode reaction is due to metal 201040314 == . Therefore, in order to improve the resistance of the steel plate, the oxidation and reduction reactions of the anode and cathode of the financial system can be considered.
。於本發明中，抑料極及陰極的氧化還原反應之方法是 在金屬表面塗佈-包含有機減合物及含奴無機酸的金 屬表面處理劑’再經加熱乾燥後，該有機聽合物中的飢 離子將會轉變成鈒氧化物（相較於+5㈣離子所形成之氧化 物’此飢氧化物具有較佳之耐水解性），而有機鈒化合物中 的配位基將會與金屬材料之金屬離子產生螯合反應而於金 屬材料表面形絲溶且穩定之有機金屬螯合物，進而有效 防止腐#因子的人侵；含磷之無機酸可活化金屬材料表面 ’以增進金屬材料表面與保護膜之間的附著十生，並會與部 分的有機釩化合物之釩離子形成穩定的釩磷複合氧化物。 因此，透過本發明之金屬表面處理劑的處理，將可有效阻 隔腐姓因子的人侵’同時讓金屬材料表面具備良好的对姓 性及耐高溫性，而所形成之保護膜與金屬材料表面之間也 將具備良好的附著性。 【實施方式】 較佳地’該含有飢離子之有機飢化合物為具有至少一 配位基之有機釩化合物，該配位基是選自於羥基、叛基、 竣基、乙醯基乙酸酯或此等之一組合；更佳地，該含有釩 離子之有機釩化合物是選自於VO(C5H7〇2)2、v(C5h7〇2)3或 此專之一組合。 較佳地’基於該金屬表面處理劑之體積為1升，該含 有釩離子之有機釩化合物的用量範圍為5〜20 g/L。當該有 5 201040314 機叙化合物的含量低於5 g/L時，雖然仍可形成一保護膜， 但該保護臈的耐蝕性不佳；當含量高於2〇 g/L時，將致使 金屬表面處理劑的溶解性不佳而產生沉澱情形。 較佳地’該含填之無機酸是選自於填酸、聚碟酸、偏 構酸或此等之一組合。 較佳地，基於該金屬表面處理劑之體積為丨升，該含 有磷之無機酸的用量範圍為1〇〜30 g/L。當該含有磷之無機 酸的含量低於10 g/L時，將致使金屬表面處理劑的溶解度 不佳，更影響所形成之保護膜與金屬材料表面之間的附著 性；當含量高於30 g/L時，會讓金屬材料表面過度活化而 影響到所形成之保護膜及耐蝕性。 較佳地，該金屬表面處理劑更包含一矽烷偶合劑。矽 烷偶合劑在水解縮合後’將與金屬材料表面形成Si-〇-M(M 表示金屬）的化學鍵結’使保護膜與金屬材料表面之間具有 良好的附著性，讓保護膜的整體結構更為緻密。 該矽烷偶合劑可為任何用於處理金屬材料表面之矽烷 偶合劑’較佳地’該矽烷偶合劑是選自於胺基丙基三甲氧 基矽烷、γ-胺基丙基三乙氧基矽烷、γ-環氧丙烷基丙基三曱 氧矽烷、γ-環氧丙烷基丙基三乙氧基矽烷、Ν-β(胺基乙基）-γ-胺基丙基甲基二乙氧基矽烷、Ν-β(胺基乙基）_γ_胺基丙基 三甲氧基矽烷、Ν-β(胺基乙基）-γ-胺基丙基三乙氧基矽烷、 γ-環氧丙烧基丙基甲基二乙氧基石夕烧或此等之一組合。 較佳地’基於該金屬表面處理劑之體積為1升，該矽 烷偶合劑的用量範圍為4〜20 g/L。當矽烷偶合劑的用量低 201040314 於4 g/L時’雖然仍會於金屬材料表面上形成一保護膜，但 是此保護膜的耐蝕性及附著性並不佳；當矽烷偶合劑的用 量超過20 g/L時，該保護膜的耐蝕性及耐高溫性也會變得 不佳。. In the present invention, the redox reaction of the suppressor and the cathode is carried out by coating the metal surface with a metal surface treatment agent comprising an organic subtractive compound and a slave inorganic acid, and then drying the organic compound after heating and drying. The hunger ions will be converted into cerium oxide (the oxide formed by the +5 (tetra) ion', which has better hydrolysis resistance), and the ligand in the organic cerium compound will be combined with the metal material. The metal ion generates a chelate reaction and forms a silky and stable organometallic chelate on the surface of the metal material, thereby effectively preventing the human factor of the rot factor; the inorganic acid containing phosphorus can activate the surface of the metal material to enhance the surface of the metal material. The adhesion between the protective film and the protective film forms a stable vanadium-phosphorus composite oxide with vanadium ions of a part of the organic vanadium compound. Therefore, through the treatment of the metal surface treatment agent of the present invention, the person who can effectively block the rot factor can be invaded while the surface of the metal material has a good surname and high temperature resistance, and the protective film and the surface of the metal material are formed. There will also be good adhesion between them. [Embodiment] Preferably, the organic hunger compound containing a hunger ion is an organovanadium compound having at least one ligand selected from the group consisting of a hydroxyl group, a thiol group, a thiol group, and an ethyl decyl acetate. Or a combination of the above; more preferably, the vanadium ion-containing organovanadium compound is selected from the group consisting of VO(C5H7〇2)2, v(C5h7〇2)3 or a combination thereof. Preferably, the volume of the metal surface treatment agent is 1 liter, and the vanadium ion-containing organic vanadium compound is used in an amount ranging from 5 to 20 g/L. When the content of the compound having 5 201040314 is less than 5 g/L, although a protective film can still be formed, the corrosion resistance of the protective ruthenium is not good; when the content is higher than 2 〇g/L, the metal is caused The surface treatment agent has poor solubility and causes precipitation. Preferably, the filler-containing mineral acid is selected from the group consisting of acid-filling, poly-disc acid, partial acid or a combination thereof. Preferably, the amount of the inorganic acid containing phosphorus is in the range of 1 Torr to 30 g/L, based on the volume of the metal surface treating agent. When the content of the inorganic acid containing phosphorus is less than 10 g/L, the solubility of the metal surface treatment agent is poor, and the adhesion between the formed protective film and the surface of the metal material is more affected; when the content is higher than 30 When g/L, the surface of the metal material is excessively activated to affect the formed protective film and corrosion resistance. Preferably, the metal surface treatment agent further comprises a decane coupling agent. After the hydrolysis and condensation, the decane coupling agent will form a chemical bond with Si-〇-M (M for metal) on the surface of the metal material to make the protective film and the surface of the metal material have good adhesion, and the overall structure of the protective film is further improved. For the sake of density. The decane coupling agent may be any decane coupling agent for treating the surface of the metal material. Preferably, the decane coupling agent is selected from the group consisting of aminopropyltrimethoxydecane and gamma-aminopropyltriethoxydecane. , γ-propylene oxide propyl trioxoxane, γ-propylene oxide propyl triethoxy decane, Ν-β (aminoethyl)-γ-aminopropyl methyl diethoxy矽, Ν-β(aminoethyl)_γ-aminopropyltrimethoxydecane, Ν-β(aminoethyl)-γ-aminopropyltriethoxydecane, γ-epoxypropane A propyl propyl diethoxylate or a combination of these. Preferably, the volume of the metal surface treatment agent is 1 liter, and the oxane coupling agent is used in an amount ranging from 4 to 20 g/L. When the amount of decane coupling agent is low at 201040314 at 4 g/L, although a protective film is still formed on the surface of the metal material, the corrosion resistance and adhesion of the protective film are not good; when the amount of the decane coupling agent exceeds 20 When g/L, the corrosion resistance and high temperature resistance of the protective film also become poor.
較佳地’該金屬表面處理劑具有1.5~5.〇之pH值範圍 。當pH值低於丨.5時，將致使金屬材料表面上之保護膜的 耐蝕性不佳而影響表面外觀；而當pH值高於5 〇時，金屬 表面處理劑較不穩定且容易形成沉澱物。該金屬表面處理 劑可透過習知方式來調整pH值，例如可視需要增減該含磷 之無機酸的用量，或者另外利用鹼液來調整。 本發明之金屬材料的表面處理方法是藉由將上述金屬 表面處理劑塗佈於一金屬材料表面而完成，此塗佈方式可 採用各種已知的塗佈方式，且於塗佈之前，該金屬材料可 先進行清洗及脫脂步驟。 本發明之表面處理方法可適用於處理各種金屬材料， 較佳地，該金屬材料是選自於㈣、鋅材 '鍵鋅之騎或 鍍鋅鋁合金之鋼材。 較佳地，該表面處理方法更包含一加熱乾燥步驟。更 佳地，該加熱乾燥步驟之溫度範圍為5〇γ〜25〇Υ。 較佳地，該經表面處理之金屬材料的保護膜具有 〇·05〜2叫之膜厚；更佳地，該保護膜的模厚範圍為0.Η :。當該保護膜之膜厚不及⑽μιη冑將致使保護膜的 =性及附著性不佳；當膜厚超過2帥時，雖㈣有效提 昇耐錄，但將致使外财佳且增加製作成本。 7 201040314 本發明經表面處理之金屬材料的保護膜是以無機材料 為主’因而可讓金屬材料具有良好的对南溫性，所以將有 利於運用至高溫焊接工程。 本發明將就以下實施例來作進一步說明，但應瞭解的 是’該實施例僅為例示說明之用，而不應被解釋為本發明 實施之限制。 <實施例> 實施例1〜8 (以下標註為E1〜E8)之共同製法： 1 · 金屬表面處理劑： 依據下表1之用量及組成種類’分別將有機鈒化合 物、含磷之無機酸及選擇性添加之矽烷偶合劑加以混合， 接著再加入水，直至總體積為丨升，便可分別製得實施例 1〜8之金屬表面處理劑。 2. 經表面處理之金屬材料： 分別取一金屬材料（熱浸鍍鋅鋼板，GI)，使其表面進 行鹼脫脂處理、水洗及乾燥，然後利用#3棒塗覆器（rds 3號），將上述所製得之金屬表面處理劑塗佈於金屬材料 表面，再將經塗佈之金屬材料放置於熱環型烘箱中，分別 以板溫80。(：或1〇〇。〇進行乾燥，待乾燥—段時間，即分 別製得實施例1〜8之經表面處理之金屬材料。 比較例1〜4 (以下標註為C1〜C4)之共同製法： 1 · 金屬表面處理劑： 除了依據下表 備過程皆與實施例 1改變成分組成及用量之外，其餘製 1〜8相同，最後分別製得比較例】〜4 201040314 之金屬表面處理劑。 2· 經表面處理之金屬材料： 除了分別選用比較例1〜4之金屬表面處理劑外，其 餘製備過程皆與實施例卜8相同，最後分別製得比較例 1〜4之經表面處理之金屬材料。 [測試】 將上述實施例1〜8及比較例1〜4所製得之經表面處理 之鋼板分別進行以下測試，所得結果分別如表〗所示. 1·耐制生：㈣JIS Z-2371標準方法之鹽水喷丁霧試驗 ，在試驗72小時後，以目視評估鋼板表面之白鏽發 生面積，當白鏽發生面積越小時，表示耐蝕性越佳 。若白鏽發生面積2 50%則判定耐蝕性不佳，標註為 「X」；若30%$白鏽發生面積$5〇%，則判定耐蝕性 差，標註為「△」；若10%$白鏽發生面積， 則判定耐蝕性尚可’標註為「〇」：若白鏽發生面積 < 10%，則判定耐蝕性佳，標註為「◎」。 2·附著性：在實施例1〜8及比較例1〜4所製得之經表 面處理之鋼板表面上，分別塗佈壓克力塗料及醇酸 樹知塗料，接著再烘烤乾燥，以於鋼板表面上另形 蜊試層。然後分別於測試層之中央用切割刀刻 劃寬為1 mm之百格棋盤目，並進行黏膠剝離試驗即 =未剝離之棋盤目之殘有數評估保護膜之附著性。 田殘有數為95以上時，則具有不錯的附著性。 3·耐巧溫性··將實施例1〜8及比較例1〜4所製得之經 9 201040314 表面處理之鋼板於高溫環境（4〇〇°C)靜置5分鐘， 接著以目視評估鋼板表面之外觀’評估標準如下： ◎.南溫試驗後之鋼板表面外觀與未經高溫試驗之 鋼板表面外觀相同。 〇：高溫試驗後之鋼板表面外觀較未經高溫試驗之 鋼板表面外觀有些微差異。 △:高溫試驗後之鋼板表面外觀較未經高溫試驗之 鋼板表面外觀有明顯黃化或暗化現象。 X:高溫試驗後之鋼表面外觀較未經高溫試驗之 鋼板表面外觀㈣顯黃化或暗化現象，且鋼板 表面有明顯龜裂紋路。 10 201040314 表1 有機奴化 合物 (用量g/L) 磷酸用 量(g/L) 檸檬酸用 量(g/L) 矽烷偶合劑 (用量g/L) pH值 板溫 (°C) 耐勉性 附著性 (AC/AD) 财南溫 性 E1 la⑺ 10 - 2.02 100 〇 100/100 ◎ E2 Ia(20) 30 - 1.73 100 ◎ 100/100 ◎ E3 la⑺ 10 - IIIa(5) 2.46 100 ◎ 100/100 ◎ E4 Ia(10) 14 - IIIa(9) 2.27 100 ◎ 100/100 ◎ E5 Ia(10) 14 - IIIa(9) 2.27 80 ◎ 100/100 ◎ E6 Ia(10) 10 - IIIa(9) 3.11 100 ◎ 100/100 ◎ E7 Ia(10) 14 - Illb(ll) 2.18 100 ◎ 100/100 〇 E8 Ia(20) 30 - IIIa(20) 2.26 100 ◎ 100/100 ◎ C1 Ib(6) 12 - IIIa(8) 2.65 100 〇 95/99 ◎ C2 - 14 - IIIa(9) - 100 X 85/90 ◎ C3 Ia(20) - 53 IIIa(5) _ 100 Δ 70/60 X C4 la⑺ 10 - IIIa(78) - 100 X 90/99 Δ la為VO(C5H7〇2)2 ; lb為VOS04 ; Ilia為γ-胺基丙基三乙氧基矽 烷；Illb為γ-環氧丙烷基丙基三甲氧基矽烷 [結果] 由表1之結果可知，實施例1〜8皆同時具備良好的耐 蝕性、附著性及耐高溫性；而反觀比較例1〜4，並無法同 時具備上述優點。 將實施例3與比較例1進行比較時，可發現實施例3 具備相當優異的财姓性、附著性及财高溫性，而比較例1 的附著性則明顯較差，這是因為比較例1使用之voso4並 11 201040314 未具備有機配位基，以致無法與金屬離子形成有機金屬螯 δ物因此所开> 成之保護膜與金屬材料表面之間無法具備 良好附著性。將實施例4與比較例2進行比較時，可以發 現比較例2未添加有機飢化合物，使得耐勉性及附著性明 顯不佳。而實施例2與比較例3進行比較時，雖然比較例 3另添加檸檬酸及碎烧偶合劑’但耐姓性、附著性及财高 性白不佳，這是因為未添加填酸所致。將實施例3與比 較例4進行比較時，可發現比較例4雖使用較多量的石夕烧 偶合劑，但耐蝕性、附著性及耐高溫性皆不佳，這是因為 石夕燒偶合劑的用量過高所致。 综上所述，本發明金屬表面處理劑透過有機釩化合物（ 所含釩離子非為+5價）與磷酸之組合，在後續用於處理金屬 材料表面時，可於金屬材料表面形成一保護膜，使得金屬 材料具備良好的耐蝕性、附著性及耐高溫性。 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】 益 【主要元件符號說明】 無 12Preferably, the metal surface treatment agent has a pH range of 1.5 to 5. When the pH is lower than 丨.5, the corrosion resistance of the protective film on the surface of the metal material is not good and the surface appearance is affected; and when the pH is higher than 5 ,, the metal surface treatment agent is unstable and precipitates easily. Things. The metal surface treatment agent can be adjusted in a conventional manner by, for example, increasing or decreasing the amount of the phosphorus-containing inorganic acid as needed, or additionally adjusting it with an alkali solution. The surface treatment method of the metal material of the present invention is completed by coating the above metal surface treatment agent on the surface of a metal material, and the coating method can adopt various known coating methods, and before coating, the metal The material can be cleaned and degreased first. The surface treatment method of the present invention can be applied to the treatment of various metal materials. Preferably, the metal material is selected from the group consisting of (4), zinc material, zinc-bonded or galvanized aluminum alloy. Preferably, the surface treatment method further comprises a heat drying step. More preferably, the temperature of the heat drying step ranges from 5 〇 γ to 25 Torr. Preferably, the protective film of the surface-treated metal material has a film thickness of 〇·05~2; more preferably, the film thickness of the protective film ranges from 0.Η:. When the film thickness of the protective film is less than (10) μm, the protective film will have poorness and adhesion. When the film thickness exceeds 2, the film will effectively increase the resistance, but it will lead to good external profit and increase production cost. 7 201040314 The protective film of the surface-treated metal material of the present invention is mainly made of an inorganic material, and thus the metal material has a good south temperature property, so that it is advantageous for use in a high-temperature welding process. The invention is further described in the following examples, but it should be understood that the examples are merely illustrative and are not to be construed as limiting. <Examples> The common processes of Examples 1 to 8 (hereinafter referred to as E1 to E8): 1 · Metal surface treatment agent: Organic bismuth compound, phosphorus-containing inorganic substance according to the amount and composition type of the following Table 1 The metal surface treatment agents of Examples 1 to 8 were prepared by mixing the acid and the selectively added decane coupling agent, followed by the addition of water until the total volume was soar. 2. Surface-treated metal material: Take a metal material (hot-dip galvanized steel sheet, GI), make the surface degreased, wash and dry, and then use #3 rod applicator (rds No. 3). The metal surface treatment agent prepared above was applied to the surface of the metal material, and the coated metal material was placed in a hot ring type oven at a plate temperature of 80 Å. (: or 1 〇〇. 〇 drying, to be dried for a period of time, that is, the surface-treated metal materials of Examples 1 to 8 were respectively prepared. The common method of Comparative Examples 1 to 4 (hereinafter referred to as C1 to C4) : 1 · Metal surface treatment agent: The metal surface treatment agent of Comparative Example ～4 201040314 was prepared separately except that the composition and amount of the components were changed according to the following procedure, and the other compositions were the same. 2. Surface-treated metal material: Except that the metal surface treatment agents of Comparative Examples 1 to 4 were separately used, the rest of the preparation process was the same as that of Example 8 except that the surface-treated metal of Comparative Examples 1 to 4 was separately prepared. [Test] The surface-treated steel sheets prepared in the above Examples 1 to 8 and Comparative Examples 1 to 4 were respectively subjected to the following tests, and the results obtained are shown in Table 〗. 1. Resistance to production: (4) JIS Z- The salt spray smog test of the standard method of 2371, after 72 hours of the test, visually evaluate the area of white rust on the surface of the steel sheet. When the area of white rust is small, the corrosion resistance is better. If the area of white rust is 2 50% Judging resistance If the degree is not good, it is marked as "X"; if the area of 30% white rust is $5〇%, it is judged that the corrosion resistance is poor, and it is marked as "△"; if the area of 10% white rust occurs, it is judged that the corrosion resistance can be marked "〇": If the white rust occurrence area is < 10%, it is judged that the corrosion resistance is good, and it is marked as "◎". 2. Adhesion: the surface obtained by the examples 1 to 8 and the comparative examples 1 to 4 On the surface of the treated steel sheet, the acrylic paint and the alkyd tree coating are respectively coated, and then baked and dried to form a test layer on the surface of the steel sheet, and then the width of the test layer is respectively carved with a cutter. It is a 1 mm square checkerboard, and the adhesive peeling test is performed. That is, the number of the unpeeled chessboards is evaluated to determine the adhesion of the protective film. When the number of the field is 95 or more, the adhesion is good. The temperature of the steel sheet was obtained by subjecting the steel sheets obtained in Examples 1 to 8 and Comparative Examples 1 to 4 to a surface treated with 9 201040314 in a high temperature environment (4 ° C) for 5 minutes, and then visually evaluating the surface of the steel sheet. Appearance 'evaluation criteria are as follows: ◎. Surface appearance of steel plate after south temperature test and no high temperature test The surface of the steel plate has the same appearance. 〇: The surface appearance of the steel plate after the high temperature test is slightly different from the surface appearance of the steel plate without the high temperature test. △: The surface appearance of the steel plate after the high temperature test is significantly yellower than the surface appearance of the steel plate without the high temperature test. Darkening phenomenon X: The surface appearance of the steel after the high temperature test is yellower or darker than the surface appearance of the steel plate without the high temperature test, and there is a clear crack path on the surface of the steel plate. 10 201040314 Table 1 Organic slave compound (dosage g /L) Phosphoric acid dosage (g/L) Citric acid dosage (g/L) decane coupling agent (dosage g/L) pH plate temperature (°C) 勉 附着 adhesion (AC/AD) 财南温性 E1 La(7) 10 - 2.02 100 〇100/100 ◎ E2 Ia(20) 30 - 1.73 100 ◎ 100/100 ◎ E3 la(7) 10 - IIIa(5) 2.46 100 ◎ 100/100 ◎ E4 Ia(10) 14 - IIIa(9) 2.27 100 ◎ 100/100 ◎ E5 Ia(10) 14 - IIIa(9) 2.27 80 ◎ 100/100 ◎ E6 Ia(10) 10 - IIIa(9) 3.11 100 ◎ 100/100 ◎ E7 Ia(10) 14 - Illb(ll) 2.18 100 ◎ 100/100 〇E8 Ia(20) 30 - IIIa(20) 2.26 100 ◎ 100/100 ◎ C1 Ib(6) 12 - IIIa(8) 2.65 100 〇95/99 C2 - 14 - IIIa(9) - 100 X 85/90 ◎ C3 Ia(20) - 53 IIIa(5) _ 100 Δ 70/60 X C4 la(7) 10 - IIIa(78) - 100 X 90/99 Δ la is VO(C5H7〇2)2; lb is VOS04; Ilia is γ-aminopropyltriethoxydecane; Illb is γ-propylene oxide propyltrimethoxydecane [Results] From the results of Table 1, it is known that Each of Examples 1 to 8 has good corrosion resistance, adhesion, and high temperature resistance. However, in Comparative Examples 1 to 4, the above advantages are not simultaneously provided. When Example 3 was compared with Comparative Example 1, it was found that Example 3 had a relatively excellent property name, adhesion, and high-temperature property, and the adhesion of Comparative Example 1 was remarkably inferior because Comparative Example 1 was used. Voso4 and 11 201040314 do not have an organic ligand, so that it is impossible to form an organic metal chelate with a metal ion, so that the protective film and the surface of the metal material do not have good adhesion. When Example 4 was compared with Comparative Example 2, it was found that Comparative Example 2 was not added with an organic hunger compound, so that the smash resistance and adhesion were not so good. When Comparative Example 2 was compared with Comparative Example 3, although Comparative Example 3 additionally added citric acid and a calcining coupler, the resistance to the surname, adhesion, and high-yield white was poor, because no acid was added. . When Comparative Example 3 was compared with Comparative Example 4, it was found that Comparative Example 4 used a relatively large amount of Shixia Burning Coupler, but corrosion resistance, adhesion, and high temperature resistance were not good, because the Shixi Burning Coupler The amount is too high. In summary, the metal surface treatment agent of the present invention can form a protective film on the surface of the metal material through the combination of the organic vanadium compound (the vanadium ion is not +5 valence) and the phosphoric acid. The metal material has good corrosion resistance, adhesion and high temperature resistance. 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 description of the diagram] Benefits [Main component symbol description] None 12