201229311 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種表面處理劑、表面處理方法及包含表 面處理劑之金屬材料，特別是一種金屬表面處理劑、金屬 表面處理方法及包含該金屬表面處理劑之金屬材料。 【先前技術】 經表面處理之金屬材料（如鍍鋅鋼板）具有良好的耐腐蝕 性、易於成型、焊接及塗漆等優點，因而被廣泛應用於家 電、電子產品、機械及建築等產業。然而，以習知鍍鋅鋼 板為例，在使用一段時間後，習知鍍辞鋼板之鍍鋅層於空 乳中（尤其是高溼熱環境中）還是會被腐蝕而形成白鏽，因 此鋼板在鍍辞後需再進行表面鈍化處理。 此外，在習知技術中常使用鉻酸鹽來進行鈍化處理但 隨著環保議題在各個產業間逐漸被大幅重視，且歐盟於 2002年已將六價鉻列為有害物質而禁止使用，所以目前鋼 板表面之處理已多數朝向無鉻鈍化處理方式進行。 以下列舉二種習知金屬表面處理之資料。 中華民國公告第TW 506996號 作法：一種金屬表面處理劑，其含有（A)釩化合物及（B) 含有至少一種選自於錯、鈦、鉬、鎢、錳或鈽之金屬的金 屬化合物。在該專利之實施例中，除了上述的（A)及（B)之 外’尚添加蝕刻劑（HF、H2ZrF6、CH3COOH、H2SiF6)。 缺點：該專利之金屬表面處理劑在耐蝕性測試之48小時 後’發現有1〇〜30%之白鏽發生面積，顯見該專利之處理 [S3 147686.doc 201229311 劑仍無法有效改善耐蝕性。此外，該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。 2.曰本專利公開第JP 2002-285346號 作法：一種經磷酸鋅處理之含鍍鋅鋼板，鍍鋅層上之塗 膜含有2%以上之鎂以及G()1〜1%之選自鎳銘銅之一種 以上元素’且附著量為0.7 g/m2以上。201229311 VI. Description of the Invention: [Technical Field] The present invention relates to a surface treatment agent, a surface treatment method, and a metal material comprising a surface treatment agent, in particular, a metal surface treatment agent, a metal surface treatment method, and a metal containing method Metal material for surface treatment agent. [Prior Art] Surface-treated metal materials (such as galvanized steel sheets) are widely used in home appliances, electronics, machinery, and construction industries because of their good corrosion resistance, ease of molding, soldering, and painting. However, taking a conventional galvanized steel sheet as an example, after a period of use, the galvanized layer of the conventional plated steel sheet is still corroded to form white rust in the empty milk (especially in a high humidity environment), so the steel sheet is Surface passivation treatment is required after plating. In addition, in the prior art, chromate is often used for passivation treatment, but as environmental issues are gradually taken seriously among various industries, and the European Union has banned the use of hexavalent chromium as a harmful substance in 2002, the current steel plate The treatment of the surface has been carried out mostly towards a chromium-free passivation treatment. Below is a list of two known metal surface treatments. Republic of China Publication No. TW 506996 Practice: A metal surface treatment agent comprising (A) a vanadium compound and (B) a metal compound containing at least one metal selected from the group consisting of erroneous, titanium, molybdenum, tungsten, manganese or cerium. In the examples of this patent, an etchant (HF, H2ZrF6, CH3COOH, H2SiF6) is added in addition to the above (A) and (B). Disadvantages: The patented metal surface treatment agent found a surface area of white rust of 1 〇 30% after 48 hours of corrosion resistance test. It is apparent that the treatment of this patent [S3 147686.doc 201229311 agent still cannot effectively improve 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. 2. The method of JP-A-2002-285346 is a galvanized steel sheet treated with zinc phosphate, the coating film on the galvanized layer contains 2% or more of magnesium and G() 1 to 1% is selected from nickel. One or more elements of Ming copper' and the adhesion amount is 0.7 g/m2 or more.
缺點在該專利之技術中，因為暴露於高溫高濕之環境 下時，尚存在表面變黑（以下亦稱為黑變性）之問題。此 外於5亥專利之技術中’由於塗膜係含有高濃度之鎳、 鈷銅，因此具有塗膜的色調變暗之問題。 因此有必要提供一創新且具進步性的金屬表面處理 劑金屬表面處理方法及包含該金屬表面處理劑之金屬材 料，以解決上述問題。 【發明内容】 本發明提供一種金屬表面處理劑，其包括有機釩化合 物'含磷無機酸及金屬化合物。該有機釩化合物中之釩離 子氧化數不為…該金屬化合物係選自由錄、録、： 所組成之群。 本發明另提供—種利用上述之金屬表面處理劑之金屬表 面處理方法’使該金屬表面處理劑設置於一金屬本體之表 面，以形成一保護膜。 金屬本體及上述 置於該金屬本體 本發明又提供一種金屬材料，其包 之金屬表面處理劑，該金屬表面處理 147686.doc 201229311 之表面以形成一保護膜。 本發明之金屬表面處理劑、金屬表面處理方法及包含該 金屬表面處理劑之金屬材料，可有效阻隔腐㈣子的入 侵，同時讓金屬表面具有良好的耐純及耐黑變性，而由 a金屬表面處理劑所形成之保護膜與金屬表面之間亦具有 a好的附著性。並且，本發明之金屬表面處理劑不含鉻， 因此符合環保要求。 【實施方式】 在本實施例中’本發明之金屬表面處理劑包括有機叙化 合物、含磷無機酸、金屬化合物及石夕燒偶合劑。該有機鈒 化合物中之鈒離子氧化數不為+5。該有機飢化合物具有至 少一配位基》較佳地，該配位基係選自由羥基、羰基、羧 基及乙醯丙酮基所組成之群。具有配位基之有機銳化合物 係選自由vo(c5H7o2)2(乙酿丙酮氧鈒）及v(C5H7〇^〆乙醯 丙酮釩）所組成之群。 • 較佳地’當該金屬表面處理劑之體積為1升，該有機鈒 化口物之含量係為5〜3〇 g/L。當該有機鈒化合物的含量低 於5 g/L時’雖然仍可於金屬表面形成一保護膜，但該保護 膜的耐#ί·生不佳，當含量高於3〇 g/L時，將致使該金屬表 面處理劑的溶解性不佳而產生沉澱情形。 該3½無機酸係選自由嶙酸、聚碟酸及偏墙酸所組成之 群。較佳地，當兮主Z + 田μ金屬表面處理劑之體積為1升，該含磷 無機酸之含量係/T . ^ χ 為10〜50 g/L。當該含磷無機酸的含量低於 g/L時將致使金屬表面處理劑的溶解度不佳，更影響 147686.doc 201229311 所形成於金屬表面之保護膜與金屬表面之間的附著性；合 田 含量向於50 g/L時，會讓金屬材.面過度活化而影響到所形 成於金屬表面之保護膜及耐蝕性。 在本實施例中，該金屬表面處理劑中磷/釩（P/V)之莫耳 比例係為0.5/1〜30/1。較佳地，該金屬表面處理劑中磷/釩 之莫耳比例係為1 /1〜2〇/1。 該金屬化合物係選自由鎳、鈷、鋁及鎂所組成之群。該 金屬化合物係為水溶性佳之金屬鹽類。較佳地，該金屬化 合物係選自由碳酸鈷、硫酸鈷、硝酸鈷、醋酸鈷、草酸 鈷、氧化鈷、硫酸鎳、硝酸鎳、醋酸鎳、草酸鎳、氧化 鎳、硫酸鋁、硝酸鋁、醋酸鋁、氧化鋁、硫酸鎂、硝酸 錢、醋酸鎂、草酸鎂及氧化鎂所組成之群。 較佳地’當該金屬表面處理劑之體積為1升，該金屬化 合物之含篁係為1. 〇〜1 〇 g/L。當該金屬化合物的含量低於 1 0 g/L時’將致使金屬表面變黑程度改善效果不佳；當含 量高於10 g/L時，雖金屬表面變黑程度明顯減緩，但會致 使該金屬表面處理劑之耐蝕性明顯劣化。 s玄石夕烧偶合劑可為任何用於處理金屬表面之石夕烧偶合 劑。該矽烷偶合劑在水解縮合後，將與金屬表面形成Si_ 0-Μ(Μ表示金屬）的化學鍵結，使該金屬表面處理劑與金 屬表面之間具有良好的附著性’讓該金屬表面處理劑的整 體結構更為緻密。 較佳地，該矽烷偶合劑係選自由γ_胺基丙基三甲氧基矽 烷、γ-胺基丙基三乙氧基矽烷、γ-環氧丙烷基丙基三甲氧 147686.doc 201229311 石夕院、γ-環氧丙烷基丙基三乙氧基矽烷、Ν·β(胺基乙基）· γ-胺基丙基曱基二乙氧基石夕烧、Ν-β(胺基乙基）-γ_胺基丙 基三甲氧基矽烷、Ν-β(胺基乙基）-γ-胺基丙基三乙氧基石夕 烧及γ-環氧丙烷基丙基甲基二乙氧基矽烷所組成之群。 較佳地，當該金屬表面處理劑之體積為1升，該碎院偶 合劑之含量係為4〜25 g/L。當矽烷偶合劑的用量低於4 g/L 時’雖然仍會於金屬表面上形成一保護膜，但是該保護膜 的耐蝕性及附著性並不佳；當矽烷偶合劑的用量超過25 g/L時，該保護膜的耐蝕性及耐高溫性也會變得不佳。 較佳地’該金屬表面處理劑之pH值係為1_5〜5.0。當pH 值低於1 _ 5時’將致使金屬表面上由該金屬表面處理劑所 形成之保護膜的财姓性不佳而影響表面外觀；而當pH值高 於5·0時’該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多種方式來調整pH值，例如 可視需求增減該含碟無機酸的用量，或者另外使用驗液來 調整。 本發明另提供一種利用上述之金屬表面處理劑之金屬表 面處理方法’使該金屬表面處理劑設置於一金屬本體之表 面’以形成一保護獏。較佳地，在形成該金屬表面處理劑 於該金屬本體之表面前，本發明之金屬表面處理方法可另 包括一清洗及脫脂步驟，以清潔該金屬表面，另外，可再 加熱乾燥该金屬表面處理劑。較佳地，該加熱乾燥步驟之 溫度係為50〜250°C。 該金屬本體經上述之金屬表面處理方法後，即可製得本 147686.doc 201229311 發明之金屬材料，其中該金屬表面處理劑係設置於該金屬 本體之表面以形成該保護膜。較佳地，該保護膜之厚度係 為0.05〜2 μΐη。更佳地，該保護膜之厚度係為〇卜1 μηι。 當該保護膜之厚度小於〇·〇5 μιη時’將致使該保護膜的耐 蝕性及附著性不佳；當該保護膜之厚度超過2 pm時雖然 可1¾:昇耐姓性，但將致使金屬材料之外觀不佳且增加製作 成本。 在不同應用中，該金屬本體可選自鋁材、鋅材、鍍鋅之 鋼材或鍍鋅鋁合金之鋼材。關於該金屬表面處理劑之詳細 描述，請參考先前之相關說明，在此不再加以贅述。 本發明經表面處理之金屬材料，其具有無機材料（金屬 表面處理劑）形成之保護膜，因而可讓金屬材料具有良好 的耐高溫性，所以將有利於運用至高溫焊接工程。 舉例說明，鍍鋅鋼板（金屬本體）之腐蝕過程是因為金 屬表面滲入腐蝕因子（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、水等得到電子並產生OH—，使0H-濃度升高，而陽極 反應則因金屬鋅失去電子而形成辞離子。因此，在提昇鍍 鋅系鋼板的耐蝕性時，可考慮以抑制陽極及陰極之氧化還 原反應為重點。 在本發明中，係利用該金屬表面處理劑來抑制陽極及陰 極的氧化還原反應。其中，經加熱乾燥後，該有機釩化合 物中的釩離子將會轉變成釩氧化物（相較於+5價釩離子所 形成之氧化物，該釩氧化物具有較佳之耐水解性）而有 147686.doc 201229311 機釩化合物中的配位基將會與金屬本體之金屬離子產生螯 口反應，而於金屬表面形成難溶且穩定之有機金屬螯合 物’進而有效防止腐钱因子的入侵；該含碌無機酸可活化 金屬表面，以增進金屬表面與該保護膜之間的附著性並 會與部分的有機鈒化合物之鈒離子形纟穩定的飢填複合氧 化物。 再者，該金屬化合物在高溫高濕環境下，產生之難溶性 產物具備抑制腐蝕因子滲入金屬表面之腐蝕行為，因而降 低金屬表面腐蝕反應之活性及減緩金屬表面變黑程度。 因此，本發明之金屬表面處理劑、金屬表面處理方法及 包含該金屬表面處理劑之金屬材料，可有效阻隔腐蝕因子 的入，同時讓金屬表面具有良好的耐蝕性及耐黑變性， 而由該金屬表面處理劑所形成之保護膜與金屬表面之間亦 具有良好的附著性。並且，本發明之金屬表面處理劑不含 鉻，因此符合環保要求。 茲以下列實例與比較例予以詳細說明本發明，唯並不意 謂本發明僅侷限於此等實例所揭示之内容。 實例： 實例1〜11 (以下標註為E1〜E11)之共同製法： 1 ·金屬表面處理劑： 依據表1之含量及組成種類，分別將有機釩化合物、含 磷無機酸、金屬化合物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 例1〜1 1之金屬表面處理劑。 147686.doc 201229311 2·經表面處理之金屬材料： 取多個金屬本體（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本體之 表面’再將經塗佈有金屬表面處理劑之金屬本體放置於熱 循環型烘箱中，分別以板溫80°C或1 〇〇°C進行乾燥，待乾 燥一段時間，即分別製得實例1〜11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： 除了依據表1改變成分組成及用量之外，其餘製備過程 皆與實例卜11相同，最後分別製得比較例1〜4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 備過程皆與實例1〜11相同，最後分別製得比較例1〜4之經 表面處理之金屬材料。 表1 有機釩化 合物用量 (g/L) 含填無機酸 用量(g/L) 金屬化合物 用量(g/L) 矽烷偶合劑 用量(g/L) pH值 板溫(°c) E1 la⑺ 10 Ha(l) - 1.90 100 E2 Ia(30) 50 IIa(10) - 1.51 100 E3 la⑺ 10 Ha(l) IIIa(5) 2.17 100 E4 Ia(l〇) 14 IIa(2.8) IIIa(9) 2.27 ~100~ E5 Ia(10) 14 Ila⑺ IIIa(9) 2.04 100 147686.doc -10· 201229311 E6 Ia(10) 14 IIa(2.8) IIIa(9) 2.27 80 E7 Ia(10) 14 IIb(2.8) IIIa(9) 2.29 100 E8 Ia(10) 14 IIc(2.8) IIIa(9) 2.30 100 E9 Ia(10) 10 IIa(2.8) IIIa(9) 3.11 100 E10 Ia(10) 14 IIa(2.8) Illb(ll) 2.18 100 Ell Ia(25) 40 Ha(7) IIIa(21.5) 1.95 100 Cl Ib(6) 12 - Ilia ⑻ - Γ 100 C2 - 14 - IIIa(9) - 100 C3 Ia(10) 14 - IIIa(9) - 100 C4 Ia(25) 40 - IIIa(21.5) - 100 # 在表 1 中，la 為 V0(C5H702)2 ; lb 為 V0S04 ; Ila 為 Α1(Ν〇3)3 ; lib 為 Co(N〇3)2，lie 為 Ni(N03)2 ; 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石夕 烷。 [測試】 將上述實例1〜11與比較例1〜4所製得之鋼板（金屬材料） 分別進行以下測試’所得結果分別如表2所示：Disadvantages In the technique of the patent, there is a problem that the surface becomes black (hereinafter also referred to as black denaturation) when exposed to a high temperature and high humidity environment. Further, in the technique of the 5H patent, since the coating film contains a high concentration of nickel or cobalt copper, there is a problem that the color tone of the coating film becomes dark. Therefore, it is necessary to provide an innovative and progressive metal surface treatment metal surface treatment method and a metal material containing the metal surface treatment agent to solve the above problems. SUMMARY OF THE INVENTION The present invention provides a metal surface treatment agent comprising an organic vanadium compound 'phosphorus-containing inorganic acid and a metal compound. The vanadium ion oxidation number in the organic vanadium compound is not... The metal compound is selected from the group consisting of: recorded, recorded, and:. Further, the present invention provides a metal surface treatment method using the above metal surface treatment agent to provide the metal surface treatment agent on the surface of a metal body to form a protective film. The metal body and the above-described metal body are further provided with a metal material coated with a metal surface treatment agent which is surface-treated to form a protective film of 147686.doc 201229311. The metal surface treatment agent, the metal surface treatment method and the metal material containing the metal surface treatment agent of the invention can effectively block the invasion of the rot (4), and at the same time, the metal surface has good resistance to pureness and blackening resistance, and the metal is a The protective film formed by the surface treatment agent also has a good adhesion to the metal surface. Moreover, the metal surface treatment agent of the present invention does not contain chromium, and therefore meets environmental protection requirements. [Embodiment] In the present embodiment, the metal surface treatment agent of the present invention comprises an organic compound, a phosphorus-containing inorganic acid, a metal compound, and a sulphur coupling agent. The ruthenium ion oxidation number in the organic ruthenium compound is not +5. The organic hunger compound has at least one ligand. Preferably, the ligand is selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, and an acetoacetone group. The organic sharp compound having a ligand is selected from the group consisting of vo(c5H7o2)2 (ethyl acetonide) and v (C5H7 〇 〆 〆 丙酮 acetone vanadium). • Preferably, when the volume of the metal surface treating agent is 1 liter, the content of the organic oxime is 5 〜 3 〇 g/L. When the content of the organic cerium compound is less than 5 g/L, although a protective film can still be formed on the surface of the metal, the resistance of the protective film is not good, when the content is higher than 3 〇g/L, This will cause the solubility of the metal surface treatment agent to be poor to cause precipitation. The 31⁄2 inorganic acid is selected from the group consisting of citric acid, poly-acid acid and partial wall acid. Preferably, when the volume of the bismuth main Z + field μ metal surface treatment agent is 1 liter, the content of the phosphorus-containing inorganic acid is /T. ^ χ is 10 to 50 g/L. When the content of the phosphorus-containing inorganic acid is lower than g/L, the solubility of the metal surface treatment agent is poor, which affects the adhesion between the protective film formed on the metal surface and the metal surface of 147686.doc 201229311; When it is 50 g/L, the surface of the metal material is excessively activated to affect the protective film formed on the metal surface and the corrosion resistance. In the present embodiment, the molar ratio of phosphorus/vanadium (P/V) in the metal surface treatment agent is from 0.5/1 to 30/1. Preferably, the molar ratio of phosphorus/vanadium in the metal surface treatment agent is 1/3 to 2 Å/1. The metal compound is selected from the group consisting of nickel, cobalt, aluminum, and magnesium. The metal compound is a metal salt which is excellent in water solubility. Preferably, the metal compound is selected from the group consisting of cobalt carbonate, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt oxide, nickel sulfate, nickel nitrate, nickel acetate, nickel oxalate, nickel oxide, aluminum sulfate, aluminum nitrate, acetic acid. A group consisting of aluminum, aluminum oxide, magnesium sulfate, nitric acid, magnesium acetate, magnesium oxalate and magnesium oxide. Preferably, when the volume of the metal surface treatment agent is 1 liter, the lanthanide of the metal compound is 1. 〇~1 〇 g/L. When the content of the metal compound is less than 10 g/L, the effect of improving the blackening degree of the metal surface is not good; when the content is higher than 10 g/L, although the blackening degree of the metal surface is remarkably slowed, the The corrosion resistance of the metal surface treatment agent is significantly deteriorated. The smectite coupling agent can be any stone sinter coupling agent used to treat metal surfaces. After the hydrolysis and condensation, the decane coupling agent forms a chemical bond with Si_0-Μ (Μ represents a metal) on the surface of the metal, so that the metal surface treatment agent and the metal surface have good adhesion. The overall structure is more compact. Preferably, the decane coupling agent is selected from the group consisting of γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-propylene oxide propyltrimethoxy 147686.doc 201229311 Institute, γ-propylene oxide propyl triethoxy decane, Ν·β (aminoethyl)·γ-aminopropyl decyl diethoxy zebra, Ν-β (aminoethyl) - γ-aminopropyltrimethoxydecane, Ν-β(aminoethyl)-γ-aminopropyltriethoxy oxalate and γ-propylene oxide propylmethyldiethoxydecane The group formed. Preferably, when the volume of the metal surface treatment agent is 1 liter, the content of the breaker coupling agent is 4 to 25 g/L. When the amount of the decane coupling agent is less than 4 g / L, although a protective film is still formed on the surface of the metal, the corrosion resistance and adhesion of the protective film are not good; when the amount of the decane coupling agent exceeds 25 g / When L is used, the corrosion resistance and high temperature resistance of the protective film may also become poor. Preferably, the metal surface treatment agent has a pH of from 1 to 5 to 5.0. When the pH value is lower than 1 _ 5 'will cause the surface of the metal surface treated by the metal surface treatment agent to have poor property name and affect the surface appearance; and when the pH value is higher than 5.9 'the metal The surface treatment agent is less stable and tends to form a precipitate. The metal surface treatment agent can adjust the pH in various ways, for example, by increasing or decreasing the amount of the inorganic acid contained in the dish, or by additionally using a test solution. Further, the present invention provides a metal surface treatment method by using the above metal surface treatment agent to provide the metal surface treatment agent on the surface of a metal body to form a protective crucible. Preferably, before the metal surface treatment agent is formed on the surface of the metal body, the metal surface treatment method of the present invention may further comprise a cleaning and degreasing step to clean the metal surface, and further, the metal surface may be reheated and dried. Treatment agent. Preferably, the temperature of the heat drying step is 50 to 250 °C. The metal body is subjected to the above metal surface treatment method to obtain the metal material of the invention of 147686.doc 201229311, wherein the metal surface treatment agent is disposed on the surface of the metal body to form the protective film. Preferably, the protective film has a thickness of 0.05 to 2 μΐ. More preferably, the thickness of the protective film is 1 1 μηι. When the thickness of the protective film is less than 〇·〇5 μηη, the corrosion resistance and adhesion of the protective film will be poor; when the thickness of the protective film exceeds 2 pm, although the thickness of the protective film can be increased, it will cause The appearance of metal materials is poor and the manufacturing cost is increased. In various applications, the metal body may be selected from the group consisting of aluminum, zinc, galvanized steel or galvanized aluminum. For a detailed description of the metal surface treatment agent, please refer to the previous related description and will not be repeated here. The surface-treated metal material of the present invention has a protective film formed of an inorganic material (metal surface treatment agent), so that the metal material has good high temperature resistance, so that it is advantageous for application to a high temperature welding process. For example, the corrosion process of a galvanized steel sheet (metal body) is caused by the infiltration of corrosion factors (oxygen, water, chloride ions, etc.) on the metal surface, thereby inducing an electrochemical redox reaction, that is, in a cathode reaction. Oxygen, water, etc. get electrons and produce OH-, which increases the concentration of 0H-, while the anode reaction forms a reciprocating ion due to the loss of electrons in the metal zinc. Therefore, in order to improve the corrosion resistance of the galvanized steel sheet, it is considered to focus on suppressing the oxidation reduction reaction of the anode and the cathode. In the present invention, the metal surface treatment agent is used to suppress the redox reaction of the anode and the cathode. Wherein, after heating and drying, the vanadium ions in the organic vanadium compound will be converted into vanadium oxide (the vanadium oxide has better hydrolysis resistance than the oxide formed by the +5-valent vanadium ion) 147686.doc 201229311 The ligand in the vanadium compound will react with the metal ion of the metal body to form a chelate reaction, and form a poorly soluble and stable organometallic chelate on the metal surface, thereby effectively preventing the invasion of the rotten factor; The sulphur-containing inorganic acid activates the surface of the metal to enhance the adhesion between the metal surface and the protective film and to form a hunger-filled composite oxide which is stable with a portion of the organic cerium compound. Further, the metal compound is in a high-temperature and high-humidity environment, and the poorly soluble product has corrosion behavior for inhibiting the penetration of the corrosion factor into the metal surface, thereby reducing the activity of the metal surface corrosion reaction and slowing down the blackening of the metal surface. Therefore, the metal surface treatment agent, the metal surface treatment method and the metal material containing the metal surface treatment agent of the invention can effectively block the entry of the corrosion factor, and at the same time, the metal surface has good corrosion resistance and blackening resistance. The protective film formed by the metal surface treatment agent also has good adhesion to the metal surface. Further, the metal surface treatment agent of the present invention does not contain chromium, and therefore meets environmental protection requirements. The invention is illustrated in the following examples and comparative examples, but is not intended to be limited to the scope of the invention. Example: Examples 1 to 11 (hereinafter referred to as E1 to E11) common method: 1 · Metal surface treatment agent: According to the content and composition of Table 1, organic vanadium compounds, phosphorus-containing inorganic acids, metal compounds and selectivity The metal surface treatment agent of Examples 1 to 1 was separately prepared by mixing the added decane coupling agent and then adding water until the total volume was soar. 147686.doc 201229311 2. Surface-treated metal material: Take a plurality of metal bodies (hot-dip galvanized steel sheet, GI), subject the surface to alkali degreasing, water washing and drying, and then use #3 bar coater (RDS) No. 3), the metal surface treatment agent prepared above is applied to the surface of the metal body', and the metal body coated with the metal surface treatment agent is placed in a heat cycle type oven at a plate temperature of 80 ° C, respectively. Or drying at 1 ° C for a period of time to dry, that is, the surface-treated metal materials of Examples 1 to 11 were separately prepared. Comparative methods 1 to 4 (hereinafter referred to as C1 to C4) common method: 1. Metal surface treatment agent: In addition to changing the composition and amount according to Table 1, the rest of the preparation process is the same as Example 11 and finally made separately The metal surface treatment agents of Comparative Examples 1 to 4. 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 in Examples 1 to 11, and finally the surface-treated metal of Comparative Examples 1 to 4 was separately prepared. material. Table 1 The amount of organic vanadium compound (g / L) The amount of inorganic acid contained (g / L) The amount of metal compound (g / L) The amount of decane coupling agent (g / L) pH plate temperature (°c) E1 la (7) 10 Ha (l) - 1.90 100 E2 Ia(30) 50 IIa(10) - 1.51 100 E3 la(7) 10 Ha(l) IIIa(5) 2.17 100 E4 Ia(l〇) 14 IIa(2.8) IIIa(9) 2.27 ~100 ~ E5 Ia(10) 14 Ila(7) IIIa(9) 2.04 100 147686.doc -10· 201229311 E6 Ia(10) 14 IIa(2.8) IIIa(9) 2.27 80 E7 Ia(10) 14 IIb(2.8) IIIa(9 2.29 100 E8 Ia(10) 14 IIc(2.8) IIIa(9) 2.30 100 E9 Ia(10) 10 IIa(2.8) IIIa(9) 3.11 100 E10 Ia(10) 14 IIa(2.8) Illb(ll) 2.18 100 Ell Ia(25) 40 Ha(7) IIIa(21.5) 1.95 100 Cl Ib(6) 12 - Ilia (8) - Γ 100 C2 - 14 - IIIa(9) - 100 C3 Ia(10) 14 - IIIa(9) - 100 C4 Ia(25) 40 - IIIa(21.5) - 100 # In Table 1, la is V0(C5H702)2; lb is V0S04; Ila is Α1(Ν〇3)3; lib is Co(N〇3 2, lie is Ni(N03)2; Ilia is γ-aminopropyltriethoxydecane; and Illb is γ-propylene oxide propyltrimethoxy oxalate. [Test] The steel sheets (metal materials) obtained in the above Examples 1 to 11 and Comparative Examples 1 to 4 were respectively subjected to the following tests. The results are shown in Table 2, respectively.
1.耐蝕性：採用JIS Ζ-2371標準方法之鹽水喷霧試驗， 在忒驗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。#白鏽發生面 積^50%則駭耐触性不佳，標註為「χ」；若观^白鑛 發生面積$ 50% ’則判定耐蝕性差標註為「△」；若 1嘱白料生面積則判定耐㈣尚彳，標註為 「=」」:。若白鏽發生面積<10% ’貝㈣定耐触性佳標註為 2.附著性 在實例1〜8與比較例 〜4所製得之鋼板表面 I47686.doc t S] • 11 · 201229311 上刀别塗佈壓克力塗料及醇酸樹脂塗料 燥，以於鋼板表面 有丹供砰乾 “ 另形成一測試層。然後分別於測試層 之中央用切割刀刻劃寬為1 k j剷見馮1 mm之百格棋盤目，並 剝離試驗，即以夫釗雜夕祕加 砥仃黏膠 _ 之殘有數評估㈣膜之附 著性。當殘有數為95以上時，則具有不錯的附著性。 3·耐黑變性：將實例⑷與比較例卜4所製得之鋼板， 相同條件之試樣處理面疊合成堆積狀態於高溫⑽） 及高濕環境（飽和渥度）靜置24M、時，接著以目視評估鋼板 表面之外觀，評估標準如下： ◎:試驗後之鋼板表面外觀與未經試驗之鋼板表面外觀 無明顯差異或暗化。 〇:試驗後之鋼板表面外觀較未經試驗之鋼板表面外觀 微小差異或暗化。 △:試驗後之鋼板表面外觀較未經試驗之鋼板表面外觀 微小差異或暗化’但鋼板表面有少量析出物附著。 X:試驗後之鋼板表面外觀較未經試驗之鋼板表面外觀 有明顯暗化現象’且鋼板表面有明顯析出物附著。 表2 、 耐# 性 附著性 (AC/AD) 耐黑變性 E1 〇 100/100 ----- 〇 E2 ◎ 100/100 ~--- ◎ E3 ◎ 100/100 _ ◎ E4 ◎ 100/100 E5 〇 100/100 ◎ ^ 147686.doc 12 2012293111. Corrosion resistance: The salt spray test using the JIS Ζ-2371 standard method was used to visually evaluate the area of white rust on the surface of the steel sheet after 72 hours of inspection. The smaller the area where white rust occurred, the better the corrosion resistance. #白锈 occurrence area^50%, the 骇 骇 骇 , , , , , , , , , , ; ; ; ; ; ; ; ; ; ; ; ; 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白Then judge the resistance (4), and mark it as "="":. If the white rust occurrence area <10% 'Bei (four) set the good contact resistance is marked as 2. Adhesion in the steel plate surface I47686.doc t S] • 11 · 201229311 obtained in Examples 1 to 8 and Comparative Example ～4 The knife is coated with acrylic paint and the alkyd resin coating is dry, so that the surface of the steel plate has a dan to dry. "Another test layer is formed. Then the cutter is used to scribe the width of the test layer at the center of the test layer. 1 mm of the checkerboard, and the peeling test, that is, the adhesion of the 以 夕 秘 秘 砥仃 砥仃 砥仃 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3. Blackening resistance: When the steel sheets obtained in the example (4) and the comparative example 4 are treated in the same condition, the sample is stacked and stacked in a high temperature (10)) and the high humidity environment (saturated temperature) is allowed to stand at 24 M. Next, the appearance of the steel sheet surface was visually evaluated. The evaluation criteria were as follows: ◎: The surface appearance of the steel sheet after the test was not significantly different or darkened from the surface appearance of the untested steel sheet. 〇: The surface appearance of the steel sheet after the test was lower than that of the untested steel sheet. The surface appearance is slightly different or darkened. △: Trial The surface appearance of the steel plate after inspection is slightly different or darkened than the surface appearance of the untested steel plate. However, a small amount of precipitates adhered to the surface of the steel plate. X: The surface appearance of the steel plate after the test is significantly darker than that of the untested steel plate. 'And the surface of the steel plate has obvious precipitates attached. Table 2, resistance #性性性(AC/AD) Blackening resistance E1 〇100/100 ----- 〇E2 ◎ 100/100 ~--- ◎ E3 ◎ 100 /100 _ ◎ E4 ◎ 100/100 E5 〇100/100 ◎ ^ 147686.doc 12 201229311
由表2之結果可知，音~~From the results of Table 2, the sound ~~
良好的耐#性、附著性及❹β製得之鋼板皆同時具備 得之鋼板，其具反㈣較例1〜4所製 差之耐蝕性、附著性及耐黑變性。 將實例3與比較例1推j 進仃比較時，可發現實例3所製得之 鋼板具備相當優異The steel plates made of good resistance, adhesion and ❹β are all available at the same time. They have the opposite corrosion resistance, adhesion and blackening resistance compared with those of Examples 1 to 4. When Example 3 was compared with Comparative Example 1, it was found that the steel sheet obtained in Example 3 was quite excellent.
慢呉的耐蝕性、附著性及耐黑變性；而比較 例1所製得之鋼板的性質皆明顯較差。這是因為比較例1使 用之VOSG4ii未具備有機配位基以致無法與金屬離子形 成有機金屬f合物，因此所形成之保護膜與金屬表面之間 無法具備良好耐蝕性，i比較例1未添加金屬化合物則導 致财黑變性不佳。 另將實例4與比較例2所製得之鋼板進行比較時，可以發 現比較例2未添加有機釩化合物及金屬化合物，使得耐蝕 性及对黑變性明顯不佳。再將實施例4與比較例3所製得之 鋼板進行比較時，比較例3未添加金屬化合物，則耐黑變 性明顯不佳且表面含有析出物；將實例4及比較例3之黑變 試驗後’其表面經掃描式電子顯微鏡（SEM)實際觀察結果 IS] 147686.doc • 13· 201229311 顯不’比較例3所製得之鋼板的表面明顯覆蓋析出物，該 析出物經能量散佈分析儀（EDS)半定量分析為鋅之⑽產 物。再將實例11與比較例4所製得之鋼板進行比較時，可 發現比較例4耐黑變性明顯不佳且表面含有析出物（同比較 例3之結果）。 综上所述，本發明之金屬表面處理劑、金屬表面處理方 法及包含該金屬表面處理劑之金屬材料，確實可使金屬表 面具有良好的耐蝕性及耐黑變性’而由該金屬表面處理劑 所形成之保護膜與金屬表面之間亦具有良好的附著性。 上述實施例僅為說明本發明之原理及其功效，並非限制 本發明，因此習於此技術之人士對上述實施例進行修改及 變化仍不脫本發明之精神。本發明之權利範圍應如後述之 申請專利範圍所列。 【圖式簡單說明】 (無圖式簡單說明） 【主要元件符號說明】 (無元件符號說明） 147686.doc • 14·The corrosion resistance, adhesion and blackening resistance of the slow enthalpy; and the properties of the steel sheets obtained in Comparative Example 1 were significantly inferior. This is because the VOSG 4ii used in Comparative Example 1 does not have an organic ligand so that it cannot form an organometallic compound with a metal ion, so that the formed protective film and the metal surface cannot have good corrosion resistance, i Comparative Example 1 is not added. Metal compounds lead to poor denaturation of the black. Further, when the steel sheets obtained in Example 4 and Comparative Example 2 were compared, it was found that the organic vanadium compound and the metal compound were not added in Comparative Example 2, so that the corrosion resistance and the blackening resistance were remarkably poor. When the steel sheets obtained in Example 4 and Comparative Example 3 were compared, Comparative Example 3 was not added with a metal compound, and the blackening resistance was remarkably poor and the surface contained precipitates; the blackening test of Example 4 and Comparative Example 3 was carried out. After the 'the surface of the scanning electron microscope (SEM) actual observation results IS] 147686.doc • 13· 201229311 shows that the surface of the steel plate produced by Comparative Example 3 clearly covers the precipitate, the precipitate is passed through the energy dispersion analyzer The (EDS) semi-quantitative analysis is the zinc (10) product. Further, when Comparative Example 11 was compared with the steel sheet obtained in Comparative Example 4, it was found that Comparative Example 4 was significantly inferior in blackening resistance and contained precipitates on the surface (as a result of Comparative Example 3). In summary, the metal surface treatment agent, the metal surface treatment method and the metal material containing the metal surface treatment agent of the present invention can ensure good corrosion resistance and blackening resistance of the metal surface by the metal surface treatment agent The formed protective film also has good adhesion to the metal surface. The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the scope of the present invention. The scope of the invention should be as set forth in the appended claims. [Simple description of the diagram] (Simple description of the diagram) [Explanation of main component symbols] (No description of component symbols) 147686.doc • 14·