201120245 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種金屬表面處理用組成物、金屬表面處 理方法以及金屬材料的塗裝方法。 【先前技術】 以往’爲了提高金屬表面的耐腐蝕性，通常進行鉻酸 鹽處理和磷酸鹽處理。然而近年來，鉻的毒性正成爲一個 社會問題，使用鉻酸鹽的表面處理方法也存在有處理步驟 中的鉻酸鹽煙塵飛散的問題.、排水處理設備需要極高的費 用以及鉻酸從化學轉換處理的皮膜中溶出而產生的問題 等。 此外，在磷酸鹽處理中，通常進行磷酸鋅類、磷酸鐵 類的表面處理，而爲了賦予耐腐蝕性，在磷酸鹽處理後， 通常使用鉻酸進行漂洗處理，因此存在有鉻處理的問題， 同時還存在磷酸鹽處理劑中的反應催化劑和金屬離子等的 排水處理、金屬離子從被處理金屬中溶出而產生的淤渣處 理等問題。 對此，作爲鉻酸鹽處理或磷酸鹽處理以外的處理方 法，已知有鉻類或鈦類的表面處理劑。例如，在日本特開 200 3-155578號公報中，提出了一種實質上不含有磷酸離 子，而含有鉻離子和/或鈦離子，以及氟離子的鐵和/或鋅類 基材用化學轉換處理劑。在國際公開第02/103080號文獻 中，公開了藉由使用含有（I)含有選自Ti、Zr、Hf和S!中 -4- 201120245 的至少一種金屬元素的化合物，和（π)作爲氟離子供給源的 含氟化合物的金屬表面處理用組成物，在含有鐵或鋅的至 少一種的金屬表面，可以使耐腐蝕性優良的表面處理皮膜 析出’並且由於不需要表面調整（表調）步驟，可縮短處理 步驟，實現空間的節省。 此外，在日本特開2003-253461號公報中，公開了一種 含有锆離子和/或鈦離子、氟離子和可溶性環氧樹脂，以及 實質上不含磷酸離子，並且pH爲2.5〜4.5的鐵類基材用金 屬表面處理用組成物。 此外，在日本特開2005-2370號公報中，公開了一種 鋁類基材的表面處理方法，其特徵在於由使用含有氟和鍩 的化合物所形成的化學轉換處理劑進行化學轉換處理，從 而在鋁類基材表面上形成化學轉換皮膜的步驟（1)，和使用 親水處理劑形成親水皮膜的步驟（2)組成，並且前述化學轉 換處理反應是藉由電解處理進行化學轉換處理。 此外，在日本特開2006-255540號公報中，公開了一種 在金屬材料表面上設置含有鉻和/或鈦的氧化物和/或氫氧 化物的非晶質表面處理處理層，作爲粉體塗裝或固體潤滑 塗裝的基底處理的塗裝方法。 然而，在使用任一所述的表面處理用組成物時，存在 有無法獲得與鉻酸鹽處理或磷酸鋅處理相當的耐腐蝕性， 並且與處理後藉由塗裝步驟所形成的塗膜的附著性也不充 分的情況。 201120245 【發明內容】 本發明的目的在於提供一種金屬表面處理用組成物、 金屬表面處理方法以及金屬材料的塗裝方法，該金屬表面 處理用組成物可以形成處理皮膜，該處理皮膜獲得與鉻酸 鹽處理或磷酸鹽處理相當的耐腐蝕性，並且可以形成與處 理後藉由塗裝步驟所形成的塗膜的附著性也非常優良的皮 膜。 作爲實現上述本發明目的的手段，可以提供如下的 [1] 、 [2] 、 [3]。 [1] 提供一種金屬表面處理用組成物的發明，其特徵在 於含有（A)鈦化合物和/或锆化合物 '以及（B)胺基矽烷（bl) 和多矽烷基官能性矽烷（b 2)的縮合反應物。 [2] 提供一種金屬表面處理方法的發明，其包括使含有 該[1]所述的金屬表面處理用組成物的金屬表面處理液與 金屬材料接觸的處理液接觸步驟、以及對經過了前述處理 液接觸步驟的金屬材料進行水洗的水洗步驟。 [3] 提供一種金屬材料的塗裝方法的發明，其特徵在於 包括使含有[1]所述的金屬表面處理用組成物的金屬表面 處理液與金屬材料接觸的處理液接觸步驟、對經過了前述 處理液接觸步驟的金屬材料進行水洗的水洗步驟、以及在 所彳守的表面處理皮膜層上塗裝燒結塗料（π)的塗裝步驟。 以下對本發明的實施方式進行說明。 201120245 在本發明中，鈦化合物和/或锆化合物（A)，是用於在 金屬材料表面上形成含有鈦和/或锆的化學轉換皮膜而配 合的物質，並且在將含有本發明組成物的金屬表面處理液 與金屬材料接觸時，可以使含有鈦和/或锆的氧化物和/或氫 氧化物的化學轉換皮膜層析出至金屬材料表面。 作爲這種鈦化合物和/或銷化合物（A)，通常含有選自 鈦的鹵化物及其鹽、鍩的鹵化物及其鹽、碳酸锆及其鹽、 以及硝酸鉻中的至少一種化合物，並較佳爲含有選自氟化 鍩、氟化鈦、碳酸鉻及其鹽' 以及硝酸銷中的至少一種化 合物。 作爲其具體例，可以列舉例如，氟锆酸、氟化鉻鈉、 氟化锆鉀、氟化锆鋰、氟化锆銨、碳酸锆、硝酸锆、氟鈦 酸、氟化鈦鈉、氟化鈦鉀、氟化鈦鋰、氟化鈦銨等。其中， 特別較佳爲硝酸锆、氟化锆銨、氟化鈦銨。 在本發明組成物中，鈦和/或锆化合物（A)的含量，以 金屬元素換算爲5〜lOOOOppm，較佳爲20〜2000ppm，並進 一步較佳爲50〜500ppm的範圍，這從確保金屬材料表面上 析出的皮膜量，以及經濟性等觀點考慮是較佳的。 在本發明中，胺基矽烷（bl)和多矽烷基官能性矽烷（b2) 的縮合反應物（B)，是用於提高皮膜的耐腐蝕性，以及提高 與處理後藉由塗裝步驟所形成的塗膜的附著性而配合的物 質，並且其通常可以藉由使胺基矽烷（bl)和多矽烷基官能 性矽烷（b2)在水、醇或酸性水溶液等中進行水解而得到。 201120245 在使用酸進行水解時，可以使用例如鹽酸、乙酸、硫酸、 磷酸、磺酸等。 作爲胺基矽烷（b 1 )，可以列舉例如，3 -胺基丙基三甲氧 基矽烷、3 -胺基丙基三乙氧基矽烷、3 -胺基丙基甲基二乙 氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙 基）-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基）-3-胺基丙基 三乙氧基矽烷等。 多矽烷基官能性矽烷（b 2)，較佳爲由下述通式（I)表示。 (X1 ka-b(R1 )a(R2)bSi-Y-Si(R3)c(R4)d(X2)3.c-d ..(1) (式（I)中，R1、R2、R3和R4獨立地表示氫原子或碳原 子數爲1〜30的1價的有機基團。Y表示2價的有機基團 或胺。X1和X2獨立地表示水解性基團。a和b獨立地表示 0、1或2，並且0Sa + bS2。c和d獨立地表示〇、1或2, 並且 0 S c + d S 2。） 上述中，R1、R2、R3和R4獨立地表示氫原子或碳原子 數爲1〜30的1價的有機基團。作爲1價的有_基團，可 以列舉烷基、烯基、環烷基、芳基等烴基；具有羥基、環 氧基、胺基等官能基的烴基等，並特佳爲甲基、乙基等低 級院基。 在上述中，Y表示2價的有機基團或胺。作爲2價的 有機基團，可以列舉伸烷基 '伸烷基醚基和伸烷基硫醚基、 或含有這些基團作爲部分結構的基團，並特佳爲伸烷基。 此等之碳原子數爲2〜30，並特佳爲2〜12。 201120245 在上述中，χ1和χ2表示水解性基團。作爲水解性基團， 可以列舉碳原子數爲1〜4的烷氧基’並特佳爲甲氧基、乙 氧基。此外，a + b和c + d都較佳爲0或1。 作爲上述多矽烷基官能性矽烷（b2)的具體例，可以列 舉例如，二（三甲氧基矽烷基）甲烷、二（三甲氧基矽烷基） 乙院、1,2 -二（二乙氧基砂院基）乙垸、1,2 - 一（三甲氧基砂院 基）乙烷、二（三乙氧基矽烷基）己烷、二（三甲氧基矽烷基） 己院、1,9 -二（二乙氧基砍院基）壬院、1,9 -二（三甲氧基砂院 基）壬院、1, 8 -二C二乙氧基政院基）辛院、二（三甲氧基政院 基）胺、二（三乙氧基矽烷基）胺、二（三乙氧基矽烷基甲基） 胺、二（三乙氧基矽烷基丙基）胺等，其中，從操作安全性、 提高皮膜的耐腐蝕性、提高與塗膜的附著性等觀點考慮， 較佳爲1,2-二（三乙氧基矽烷基）乙烷。 上述胺基矽烷（bl)和多矽烷基官能性矽烷（b2)的使用 比例’以莫耳比計爲50/50〜99/1，較佳爲70/30〜99/1，並 進一步較佳爲80/20〜95/5的範圍，這從防止製造時的凝膠 化、提高皮膜的耐腐蝕性、經濟性等觀點考慮是較佳的。 本發明中’在製造縮合反應物（B)時，除了上述胺基矽 烷（bl)和多矽烷基官能性矽烷（b2)外，還可以根據需要適當 添加除前述以外的有機矽烷（b3)。 作爲這種有機矽烷（b3)，可以列舉例如，甲基三甲氧 基矽烷 '甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三 乙氧基矽烷、2-(3,4環氧基環己基）乙基三甲氧基矽烷、乙 201120245 烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、對苯乙燒基三 甲氧基矽烷、3 -甲基丙烯醯氧基丙基甲基二甲氧基矽院' 3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基 丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基 矽烷、3 -丙烯醯氧基丙基三甲氧基矽烷、3 -氯丙基三甲氧 基矽烷、3-毓基丙基甲基二甲氧基矽烷、3-锍基丙基三甲 氧基矽烷等。從控制析出的觀點考慮，該有機矽烷（b3)在 不妨礙對溶劑的溶解性的範圍內進行使用，通常’相對於 胺基矽烷（bl)和多矽烷基官能性矽烷（b2)的總莫耳量’希望 以100莫耳％以下，較佳爲50莫耳％以下的量使用。 在本發明組成物中，（B)成分的含量，以固體成分濃度 計爲1〜5000ppm，並較佳爲20〜500ppm的範圍’适從確 保皮膜量、經濟性的觀點考慮是較佳的。 本發明組成物，從提高皮膜的耐腐蝕性、提高與塗膜 的附著性等觀點考慮，較佳爲進一步含有選自鎂、鋅、鈣、 鋁、鎵'銦、銅'鐵、錳、鎳、鈷、铈、緦'稀土類元素、 錫、鉍、釔、釩、鋇、鉻、鉬、鎢和銀構成的群組中的至 少一種金屬元素。作爲這些金屬元素的供給源’沒有特別 限定，例如，可以作爲硝酸化物、硫酸化物、或氟化物等 在化學轉換處理劑中進行配合、此外，這些金屬元素，遼 可以是例如，在處理鐵類基材、鋁類基材、鋅類基材等被 處理物時溶出的金屬離子。 -10- 201120245 在本發明組成物中，含有上述金屬元素時，其含量以 金屬元素換算，適合在0·1〜5000ppm的範圍內。 在上述金屬元素中，特別從提高與塗膜的附著性等觀 點考慮，較佳爲鎂、鋁等，並且其含量適合爲1〜5000ppm， 並較佳爲20〜2000ppm的範圍內。此外，從提高皮膜的耐 腐蝕性等觀點考慮，較佳爲銅、釩等，並且其含量適合爲 0.5〜lOOppm，並較佳爲2〜50ppm的範圍內。 本發明組成物，從進一步促進皮膜形成、提高皮膜的 耐腐蝕性等觀點考慮，可以進一步含有選自硝酸、硫酸、 磷酸 '膦酸、次磷酸以及此等之鹽構成的群組中的至少一 種。其含量，以固體成分計，適合爲1〜50000ppm，並較 佳爲5〜30000ppm的範圍內。 本發明組成物，從提高皮膜的耐腐蝕性、提高與塗膜 的附著性等觀點考慮，可以進一步含有水溶性或水分散性 有機樹脂。作爲水溶性或水分散性有機樹脂，可以列舉例 如’環氧樹脂、丙烯酸樹脂、聚酯樹脂、聚烯丙基胺樹脂、 聚乙烯基胺樹脂、聚丁二烯樹脂、聚胺基甲酸酯樹脂、聚 乙烯醇、乙烯-乙酸乙烯酯樹脂等。此外，可以根據需要適 當配合蜜胺樹脂、苯并胍胺樹脂、尿素樹脂、（封端）聚異 氰酸酯、酚醛樹脂等。 在本發明組成物中，使用上述水溶性或水分散性有機 樹脂時’從皮膜的形成性 '提高皮膜的耐腐蝕性、提高與 塗膜的附著性等觀點考慮，其含量以固體成分濃度計，希 望爲0.1〜300000pprn，並較佳爲5〜5000ppm的範圍內。 201120245 爲了進一步提高組成物的穩定性和析出性，本發明組 成物可以含有界面活性劑。作爲界面活性劑，可以列舉陰 離子類界面活性劑、陽離子類界面活性劑、非離子類界面 活性劑、兩性界面活性劑，其中，較佳爲陰離子類界面活 性劑、非離子類界面活性劑、以及倂用此等之倂用。 作爲陰離子類界面活性劑，可以列舉例如，脂肪酸鹽、 烷基硫酸酯鹽、烷基苯磺酸鹽、烷基磷酸鹽等。作爲陽離 子類界面活性劑，可以列舉例如，烷基胺鹽、四級銨鹽等。 在使用非離子類界面活性劑時，HLB爲8以上，並較 佳爲約10〜約20的範圍。另外，上述HLB表示分子中的 親水基和親油基的平衡値，並且是 Hydrophile-Lipophile Balance (親水親油平衡）的簡稱。作爲這種非離子類界面活 性劑，可以列舉例如，聚氧乙烯烷基醚、聚氧乙烯烷基芳 基醚 '聚氧乙烯衍生物、山梨聚糖脂肪酸酯、聚氧乙烯山 梨聚糖脂肪酸酯、丙三醇脂肪酸酯、聚氧乙烯脂肪酸酯、 聚氧乙烯烷基胺、烷基烷醇醯胺等。 在倂用陰離子類界面活性劑和非離子類界面活性劑 時，以兩成分的固體成分合計爲基準，陰離子類界面活性 劑/非離子類界面活性劑=99.9/0.1(質量％)〜10/90(質量 %)，並較佳爲80/20(質量％)〜50/50(質量％)的範圍。 在本發明組成物中使用上述界面活性劑時，從進行充 分的脫脂處理、經濟性等觀點考慮，其含量以固體成分濃 度計較佳爲5〜300000ppm，並更佳爲25〜l〇〇〇〇〇ppm的範 圍內。 -12- 201120245 本發明組成物的pH，較佳爲15〜6 5，並特佳爲3 〇 〜4.5的範圍。PH的調整，可以使用前述硝酸、硫酸等酸 性化合物，以及氫氧化鈉、氫氧化鉀、氨等鹼性化合物。 在本發明組成物中，除了上述成分外，可以根據需要 配合任意成分，可以列舉例如水分散性二氧化矽等二氧化 矽等。 本發明的金屬表面處理方法，包括使含有如上述所得 的金屬表面處理用組成物的金屬表面處理液與金屬材料接 觸的處理液接觸步驟、以及對經過了前述處理液接觸步驟 的金屬材料進行水洗的水洗步驟。 處理液接觸步驟沒有特別限定，例如，可以採用浸漬 法、噴霧法、輥塗法等方法。較佳爲將處理液的溫度調整 在20〜70 °C ’特別是30〜55 °C的範圍內進行處理。 作爲金屬材料’通常可以列舉鐵類基材、鋁類基材、 以及鋅類基材等。鐵' 鋁和鋅類基材，是指基材是由鐵和/ 或其合金所形成的鐵類基材、基材是由鋁和/或其合金所形 成的IS類基材、基材是由鋅和/或其合金所形成的鋅類基 材· ° Φ發明組成物，也可以用於由鐵類基材、鋁類基材、 胃類基材中的多種金屬基材所形成的被塗覆物的化學 轉換處理。本發明方法，特別較佳爲用於鐵類基材。 €@金屬材料，較佳爲在上述處理液接觸步驟前進行 ^脂處理 '脫脂後水洗處理，以及在處理液接觸步驟後進 行水洗步驟。 -13- 201120245 上述脫脂處理，用於除去附著在基材表面上的油分和 污垢，並且該處理是使用無磷、無氮脫脂洗滌液等脫脂劑， 並通常在 30〜70 °C下進行幾秒鐘〜幾分鐘左右的浸漬處 理。根據需要，也可以在脫脂處理前進行預脫脂處理。 爲了不對後面各種塗裝後的密合性、耐腐蝕性等產生 不良影響，上述處理液接觸後的水洗步驟要進行一次或更 多次。這時，最終的水洗，適合用純水進行。該水洗處理， 可以是噴霧水洗或浸漬水洗，也可以將這些方法組合起來 進行水洗。 在上述水洗步驟後，可以根據需要採用乾燥步驟。在 進行乾燥步驟時，可以進行冷風乾燥 '熱風乾燥等。 藉由本發明方法所得的皮膜，其對金屬材料的附著 量’從提高皮膜的耐腐蝕性、提高與塗膜的附著性等觀點 考慮，以處理劑中所含的金屬元素換算計，較佳爲〇1〜 2000mg/m2’ 並特佳爲 5〜200mg/m2。 在如上述所得的皮膜上，可以適當的使用以往公知的 塗料進行塗裝，形成塗膜層’並且也可以通過黏合劑層設 置有機樹脂覆蓋層。作爲塗料，可以無特別限制地使用以 往公知的塗料’其可以列舉例如，有機溶劑稀釋型塗料、 水性塗料、粉體塗料等。 此外’本發明的塗裝方法’包括使含有如上述所得的 金屬表面處理用組成物（有時將其稱爲“金屬表面處理用 組成物（1)” ）的金屬表面處理液與金屬材料接觸的處理液 -14- 201120245 接觸步驟、對經過了前述處理液接觸步驟的金屬材料進行 水洗的水洗步驟、以及在所得的表面處理皮膜層上塗裝燒 結塗料（II)的塗裝步驟。 處理液接觸步驟沒有特別限定，例如，可以採用浸漬 法' 噴霧法、輥塗法等方法。較佳爲將處理液的溫度調整 在2 0〜7 0 °C，特別是3 0〜5 5 t的範圍進行處理。 作爲金屬材料，通常可以列舉鐵類基材、鋁類基材、 以及鋅類基材等。鐵、鋁和鋅類基材，是指基材是由鐵和/ 或其合金所形成的鐵類基材、基材是由鋁和/或其合金所形 成的is類基材、基材是由鋅和/或其合金所形成的鋅類基 材。金屬表面處理用組成物（I)，也可以用於由鐵類基材、 基材 '以及鋅類基材中的多種金屬基材所形成的被塗 覆物的化學轉換處理。本發明方法，特別較佳爲用於鐵類 基材。 這些金屬材料，較佳爲在上述處理液接觸步驟前進行 '脫脂後水洗處理，以及在處理液接觸步驟後進 行水洗步驟。 ±述脫脂處理，用於除去附著在基材表面上的油分和 、污垢’並且該處理是使用無磷、無氮脫脂洗滌液等脫脂劑， 並通常在30〜70 °c下進行幾秒鐘〜幾分鐘左右的浸漬處 S °根據需要，也可以在脫脂處理前進行預脫脂處理。 爲了不對後面各種塗裝後的密合性、耐腐蝕性等不良 影響’上述處理液接觸後的水洗步驟要進行一次或更多 -15- 201120245 次。這時，最終的水洗，適合用純水進行。該水洗處理， 可以是噴霧水洗或浸漬水洗，並且可以將這些方法組合起 來進行水洗。 在上述水洗步驟後’可以根據需要採用乾燥步驟。在 進行乾燥步驟時’可以進行冷風乾燥、熱風乾燥等。 在本發明方法中’通過金屬表面處理用組成物⑴所得 的皮膜’其對金屬材料的附著量，從提高皮膜的耐腐蝕性' 提高與塗膜的附著性等觀點考慮，以處理劑中所含的金屬 元素換算計’較佳爲0.1〜2000mg/m2，並特佳爲5〜 200mg/m2。 在本發明方法的塗裝步驟中，在如上述所得的皮膜 上，塗裝燒結塗料（II)。 作爲燒結塗料（II)，可以無特別限制地使用以往公知的 燒結型塗料，其可以列舉例如，有機溶劑稀釋型塗料、水 性塗料、粉體塗料等。 作爲上述有機溶劑稀釋型塗料，可以列舉例如，以聚 酯樹脂、醇酸樹脂、環氧樹脂、丙烯酸樹脂、胺基甲酸酯 樹脂、氟樹脂、氯乙烯樹脂、以及此等之改性樹脂等作爲 基體樹脂成分，並根據需要含有可以與這些基體樹脂成分 中的羥基或環氧基等官能基反應的胺基樹脂（例如，蜜胺樹 脂等）、（封端化）聚異氰酸酯化合物、多元酸等固化劑的塗 料，其中，可以較佳爲使用聚酯/蜜胺樹脂類塗料、醇酸/ 蜜胺樹脂類塗料和丙烯酸樹脂類塗料等。 -16- 201120245 在上述有機溶劑稀釋型塗料中，進一步配合有機溶 劑’並根據需要，適當配合固化催化劑、顏料類'消泡劑' 塗面調整劑、防沉降劑、顏料分散劑、福馬林補充劑等塗 料用添加劑。 上述有機溶劑稀釋型塗料，可以通過輥塗法、噴霧塗 裝法、刷毛塗裝法、靜電塗裝法、浸漬法'簾塗法、輥塗 法等公知方法在由金屬表面處理用組成物⑴所得的皮膜上 進行塗裝，並通過乾燥形成塗膜。該塗膜的膜厚，沒有特 別限定，但通常在3〜100#m，並較佳爲15〜50μιη的範 圍進行選擇。塗膜的乾燥，根據所使用的樹脂的種類等適 當設定即可，但在對通過卷材塗布法等塗裝的材料進行連 續燒結時’通常可以在材料最高溫度爲160〜25CTC，並較 佳爲180〜230°C的條件下燒結15〜60秒鐘。在以分批式進 行燒結時’例如，也可以通過在氣體環境溫度爲80〜1 80 °C下燒結5〜60分鐘來進行。 上述粉體塗料，是將含有塗膜形成樹脂、和根據需要 添加的著色顔料或塡充顏料以及其他添加劑的塗料用組成 物熔融混煉，然後進行粉碎、粉末化的塗料，並且其可以 使用公知方法進行製造。作爲塗膜形成樹脂，可以使用一 直以來用作粉體塗料的塗膜形成樹脂的熱固性樹脂或熱塑 性樹脂等，並且該熱固性樹脂是通常所使用的。作爲這種 熱固性樹脂，可以列舉例如，（i)含羥基的固體樹脂，和具 有通過熱而與該羥基進行固化反應的官能基的固化劑的組 5p- -17· 201120245 合，（π)含羧基的固體樹脂，和具有通過熱而與該羧基進行 固化反應的官能基的固化劑的組合，（iii)含環氧基的固體 樹脂，和具有通過熱而與該環氧基進行固化反應的官能基 的固化劑的組合。此處所述樹脂的“固體” ’是指在常溫 下爲固體形狀，並較佳爲其軟化點爲80〜200 °C。此外，固 化劑可以是固體形狀，也可以是液狀，並較佳爲使用固體 形狀的物質。 作爲含羥基的固體樹脂，例如，可以使用含羥基的丙 烯酸樹脂、含羥基的聚酯樹脂等公知的用於粉體塗料的樹 脂。作爲可以與該含羥基的固體樹脂組合使用的“具有通 過熱而與該羥基進行固化反應的官能基的固化劑”，例 如，可以使用封端化的聚異氰酸酯化合物、胺基塑膠樹脂 等公知的用於粉體塗料的固化劑。作爲含羧基的固體樹 脂，例如，可以使用含羧基的丙烯酸樹脂、含羧基的聚酯 樹脂公知的用於粉體塗料的樹脂。作爲可以與該含羧基的 固體樹脂組合使用的“具有藉由熱而與該羧基進行固化反 應的官能基的固化劑”，例如，可以使用雙酚.A〜表氯醇 型環氧樹脂、脂環式環氧樹脂、酚醛清漆型環氧樹脂 '含 環氧基的丙烯酸樹脂等環氧樹脂、或羥烷基醯胺化合物等 公知的用於粉體塗料的固化劑。此外，作爲含環氧基的固 體樹脂，例如’可以使用雙酚A〜表氯醇型環氧樹脂 '脂 環式環氧樹脂、酚醛清漆型環氧樹脂 '含環氧基的丙烯酸 樹脂等公知的用於粉體塗料的樹脂。作爲可以與該含環氧 -18 - 201120245 基的固體樹脂組合使用的“具有藉由熱而與該環氧基進行 固化反應的官能基的固化劑”，例如，可以使用含羧基的 聚酯樹脂、有機酸聚醯肼化合物、咪唑化合物、二氰二胺 化合物、聚羧酸化合物、酸酐等公知的用於粉體塗料的固 化劑。 從即使燒結溫度低，形成塗膜的耐腐蝕性也良好的觀 點考慮，其中特別較佳爲含羧基的聚酯樹脂與羥烷基醯胺 化合物的組合。 上述粉體塗料，可以藉由靜電塗裝法、流動浸漬法、 噴塗法、模內裝飾法等公知方法在由金屬表面處理用組成 物（I)所得的皮膜上進行塗裝，並使用熱風爐、紅外爐、感 應加熱爐等進行燒結，而形成固化塗膜。形成塗膜的膜厚， 是燒結後的膜厚，其通常爲30〜250 #m，並較佳爲40〜 150#m的範圍爲適合的。粉體塗料的燒結條件，適合爲在 金屬材料的表面溫度爲130〜350°C，並較佳爲140〜250°C 的溫度下進行30秒鐘〜60分鐘，並較佳爲進行1〜50分鐘。 在本發明中，即使在上述塗料（Π)中，使用固化塗膜的 收縮應力高的塗料時，塗膜的附著性也優良。 此外，如上述所得的塗裝金屬板，可以是僅由上述塗 料形成塗膜的結構，也可以具有進一步適當形成面漆塗膜 的多層結構。 發明的效果 根據本發明的金屬表面處理用組成物以及金屬表面處 理方法，藉由使锆類或鈦類的表面處理劑中含有特定的矽 -19- 201120245 烷縮合反應物，可以獲得與鉻酸鹽處理或磷酸鹽處理相當 的耐腐蝕性，並且可以形成與處理後通過藉由塗裝步驟所 形成的塗膜的附著性也非常優良的皮膜。 此外’根據本發明的塗裝方法，藉由使锆類或鈦類的 表面處理劑中含有特定的矽烷縮合反應物，所得的表面處 理皮膜可以獲得與鉻酸鹽處理或磷酸鹽處理相當的耐腐蝕 性，並且與處理後藉由塗裝步驟所形成的塗膜的附著性也 非常優良。特別是在使用燒結時塗膜內會產生較大收縮應 力的燒結塗料時，也不會產生與塗膜的附著不良。 因此’本發明的塗裝方法，在家電、鋼制傢倶等工業 塗裝用途方面非常有用。 【實施方式】 實施發明之最佳型態 以下，列舉實施例更詳細地說明本發明。此外，“份” 和“ ％ ” ，只要沒有其他說明，則表示“質量份”和“質量 %” 。 矽烷縮合反應物（B)的製造 製造例1 在安裝了回流冷凝器、溫度計、氮氣導入管、攪拌機 的1L圓底燒瓶中，加入200g異丙醇、200g去離子水，開 « 始攪拌。以氣相輸入氮氣，並一邊攪拌，一邊一次性地投 入90g3-胺基丙基三甲氧基矽烷、l〇g二（三乙氧基矽烷基） 乙烷。在常溫下攪拌1小時後，在60 °C下反應6小時，然 -20- 201120245 後除去餾分，並一邊與丙二醇單甲基醚進行交換，一邊升 溫至沸點爲120°C。冷卻至60°C後，藉由減壓蒸餾進行濃 縮，得到120g生成物（P1)的不揮發成分爲40%的溶液。所 得的生成物（P1)的不揮發成分爲40 %的溶液，是無色透明的 黏稠液體。 製造例2〜1 2 除了在製造例1中，使原料組成如表1所示外，和製 造例1同樣進行，得到各生成物（P1)〜（P8)以及（R1)〜（R4)。 201120245 π嗽】 s § 200 200 m Pi 200 200 Cn pcJ \Ti m 寸 W 200 200 5 o 200 200 OO o 〇 200 200 cu g 卜 r〇 200 200 VO (X ir> 〇 ΓΛ 寸 200 200 Pu l〇 200 200 Z 200 200 m CL, 200 200 CN Oh in 200 200 5： ο 200 200 m « 减祕·5¾ fO fr ^ 111 111 s _潮g g f K： E f 9 f狴裝ΰ g f i i E ,Π Ml « «1 « _ _ u s 寧 t t _ <7 _ _ s s 瘦 盤盤 rji c|) _ rA rA Z Z Z g a ^ E： « m fr El· 祕祕 K) l· III HI 's—✓ 'w^ 11 11 遯 嫲 Ε ΠΙ m h0 1 S 1 m W l|f fr酹 ni 4 稍d： E* CN 異丙醇 去離子水 胺基矽烷(bl) 多矽烷基 官能性矽烷(b2) 有機矽烷(b3) 201120245 實施例1〜26以及比較例1〜4 金屬表面處理用組成物的製作 在上述製作的（P1)〜（P8)以及（R1)〜（R4)中，使用氟锆 酸、氟鈦酸以及各金屬的硝酸鹽等，調整具有表2所示組 成的金屬表面處理用組成物。在表2中，各金屬成分的濃 度以金屬元素換算進行表示，除此之外的成分濃度表示固 體成分濃度。 化學轉換處理以及塗裝 以市售的冷軋鋼板（SPCC-SD，日本Test Panel公司製 造，70mmxl50mmx0.8mm)、鍍鋅類鋼板（GA鋼板，日本Test Panel 公司製造，70mmxl50mmx0.8mm)、5000 系錦（日本 Test Panel 公司製造，70mmxl50mmx0.8mm)或 6000 系銘（日本 丁63〖？31^1公司製造，7〇111111\15〇111111<0.8111111)作爲基材，進行 下述所示的步驟（1)〜（4)以及表3條件下的化學轉換處理。 (1) 將上述基材在調整至40 °C的市售脫脂液中浸漬2分 鐘，進行脫脂處理後，使用自來水進行30秒鐘水洗處理。 (2) 接著，將水洗後的金屬基材，在調整至如表3所示 的pH和溫度的各實施例和比較例的金屬表面處.理用組成 物中浸漬處理10〜3 00秒鐘。使用硝酸或氫氧化鈉將pH調 整至3.2〜4.2。並且，將溫度調整至35〜50 °C。 (3) 使用自來水對上述處理後的各基材進行30秒鐘水 洗後’再用離子交換水進行30秒鐘水洗處理。接著，使用 熱風乾燥爐，在80 °C下乾燥5分鐘，形成各化學轉換處理 板0 -23- 201120245 使用“XRF1700”（島津製作所製螢光X線分析裝置）把 各化學轉換處理板的處理皮膜量當作附著金屬的合計量進 行分析。結果示於表4。 (4)在上述所得的各化學轉換處理板上進行氣體噴霧 塗裝’使“阿卡貝（音譯）RIZE” （水性聚酯聚胺基甲酸酯類 燒結型塗料）的乾燥膜厚爲30 // m，並在150°C下加熱30分 鐘進行燒結，製作各試驗塗裝板。將所得的各試驗塗裝板 提供至下述評價試驗。結果示於表4。 此外，表2中的（註1)〜（註3)如下所述。 (註1)有機樹脂：“ PAA25” ，商品名，日東紡股份有 限公司製造，聚烯丙基胺樹脂水溶液 (註2)界面活性劑：“ N e w c ο 1 1 1 0 0 ” ，商品名，日本乳 化劑股份有限公司製造，非離子類界面活性劑 (註3)二氧化矽：“Snowtex 0” ，商品名，日產化學 工業股份有限公司製造，水分散性（膠態）二氧化砂 比較例5 在市售的磷酸鋅類化學轉換處理鋼板（基材： SPCC-SD’曰本TestPanel公司製造）上進行氣體噴霧塗裝， 使“阿卡貝RIZE” （水性聚酯聚胺基甲酸酯類燒結型塗料） 的乾燥膜厚爲30/zm，並在150 °C下加熱30分鐘進行燒結， 製作試驗塗裝板。將所得的試驗塗裝板提供至下述評價試 驗。結果示於表4。 -24- 201120245 比較例6 除了在比較例5'中’使用市售的磷酸鋅類化學轉換處 理鋼板（基材：GA鋼板，日本Test Panel公司製造）外，和 比較例5同樣進行，製作試驗塗裝板。將所得的試驗塗裝 板提供至下述評價試驗。結果示於表4。 比較例7 除了在比較例5中，使用市售的鉻酸鹽類化學轉換處 理鋼板（基材：5000系鋁，日本Test Panel公司製造）外， 和比較例5同樣進行’製作試驗塗裝板。將所得的試驗塗 裝板提供至下述評價試驗。結果示於表4。 評價試驗 (*1)耐腐蝕性：對於各試驗塗裝板，用刀在塗膜上切 出深至基底的十字割痕，使其進行鹽水噴霧腐蝕試驗 (SST:根據JISZ — 2371。鹽水溫度爲35°C)240小時，然後 使用黏合帶對刀傷部分進行黏合、剝離，測定塗膜的剝離 寬度。評價基準如下所述。 ◎:未剝離 〇：剝離寬度在3mm以內 △:剝離寬度超過3mm並在5mm以內 X :剝離寬度超過5mm » (* 2)(耐水後）附著性：將各試驗塗裝板在溫水（40°C ) 中浸漬240小時，撈出後立刻在其上切出棋盤格狀（10x10 個，間隔爲1 mm)的割痕，使用黏合帶進行黏合、剝離，檢 査塗膜的剝離格個數。評價基準如下所述。 -25- 201120245 ◎:無剝離格 〇：剝離格爲5個以內 △:剝離格爲6〜1 0個 X :剝離格爲1 1個以上 -26- 20 4502 2 u«】 y m δ 堪 芻Έ 铽 S 界面活性劑(註 1)(100) 有极樹脂（註 2)(50) 二氧化矽（註 3)(100) _ 界面活性劑(註 1)(100) mmm 1 (含 ffipprn) 硝酸ροοο) S' § m 硝酸(2000) 硝酸(2000) 硝酸(2000) S' ο CS i 硝酸(2000) 1 Μ m 硝酸(2000) 硫酸(5000) 丨硝酸(1000) 硝酸(1000) 硝酸(5000) 硝酸(i oooo) Γ 硝酸(_〇) 磷酸(20> 硝酸(5000) 硝酸(5000)丨 硝酸(ιοοοο) ! 硝酸(10000) 硝酸(5000) 1 --! 硝酸(5〇〇〇) 硝酸(5000) 硝酸(5000> 次磷酸(25) 硝酸(10000) § i m Mo L里. !- ! 300 U cS CO •Λ > *Λ 〇 > «Λ Λ «Λ m 3 w *n <n 2 i ο ο 5 »ri m 6 o < 〇 ο s 〇 c3 «Λ N 200 1000 -1 500 ! «) 500 2000 500 500 500 矽院縮合反應物 (含位ppm) ο CU 1 CU P3(l〇〇) 2 ι/i CU 1 〇4 Ρ7(100) s Μ g c a PI(100) 〇 £ c c 0k Pl(100) ! E g s 1 eu c m CU Pl(50) I | PH200) P4(100) ! £ Η 1 200 ο !00 300 Ν ο ο 200 400 ο 100 o O 200 300 400 )00 200 ο 100 〇 200 200 — <s r·* »a· •ο Ό r* 00 9> o 二 2 ΤΓ «η «ο 卜 00 〇\ μ -Z(N_ 一-i·- 201120245 硝酸(2000) 硝酸(2000) 硝酸(5000) 硝酸(3000) 硝酸(5000) 硝酸(5000) W-) 〇 Ό jq 1000 1 1000 c S eu s 2 2 S g 〇 o ο § 〇 IQ — ΓΝ[Technical Field] The present invention relates to a metal surface treatment composition, a metal surface treatment method, and a metal material coating method. [Prior Art] Conventionally, in order to improve the corrosion resistance of a metal surface, chromate treatment and phosphate treatment are usually performed. However, in recent years, the toxicity of chromium is becoming a social problem. The surface treatment method using chromate also has the problem of chromate soot scattering in the processing steps. The drainage treatment equipment requires extremely high cost and chromic acid from chemistry. Problems caused by elution in the film to be converted and the like. Further, in the phosphate treatment, surface treatment of zinc phosphates and iron phosphates is usually carried out, and in order to impart corrosion resistance, after the phosphate treatment, chromic acid is usually used for rinsing treatment, and thus there is a problem of chromium treatment. At the same time, there are problems such as a reaction catalyst in a phosphate treatment agent, a drainage treatment such as metal ions, and a sludge treatment in which metal ions are eluted from the metal to be treated. On the other hand, as a treatment method other than the chromate treatment or the phosphate treatment, a surface treatment agent of chromium or titanium is known. For example, Japanese Patent Publication No. 2003-155578 proposes a chemical conversion treatment of an iron and/or zinc-based substrate containing substantially no phosphate ions and containing chromium ions and/or titanium ions and fluorine ions. Agent. In International Publication No. 02/103080, it is disclosed that by using (I) a compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and S!-4-201120245, and (π) as fluorine The metal surface treatment composition of the fluorine-containing compound of the ion supply source can precipitate a surface-treated film excellent in corrosion resistance on the surface of a metal containing at least one of iron or zinc, and since no surface adjustment (tune adjustment) step is required , can shorten the processing steps and achieve space saving. In addition, Japanese Laid-Open Patent Publication No. 2003-253461 discloses an iron containing zirconium ions and/or titanium ions, fluoride ions and soluble epoxy resins, and substantially free of phosphate ions, and having a pH of 2.5 to 4.5. A composition for metal surface treatment of a substrate. Further, Japanese Laid-Open Patent Publication No. 2005-2370 discloses a surface treatment method for an aluminum-based substrate, which is characterized in that chemical conversion treatment is carried out by using a chemical conversion treatment agent formed of a compound containing fluorine and ruthenium, thereby The step (1) of forming a chemical conversion film on the surface of the aluminum-based substrate, and the step (2) of forming a hydrophilic film using a hydrophilic treatment agent, and the chemical conversion treatment reaction described above are subjected to chemical conversion treatment by electrolytic treatment. In addition, Japanese Laid-Open Patent Publication No. 2006-255540 discloses an amorphous surface treatment layer containing an oxide and/or a hydroxide containing chromium and/or titanium on the surface of a metal material as a powder coating. A method of coating a substrate or a solid lubricant coated substrate. However, when any of the surface treatment compositions described above is used, there is a possibility that corrosion resistance equivalent to chromate treatment or zinc phosphate treatment cannot be obtained, and the coating film formed by the coating step after the treatment is used. The adhesion is not sufficient. SUMMARY OF THE INVENTION An object of the present invention is to provide a metal surface treatment composition, a metal surface treatment method, and a metal material coating method, which can form a treatment film which is obtained with chromic acid. The salt treatment or the phosphate treatment is equivalent to corrosion resistance, and it is possible to form a film which is excellent in adhesion to the coating film formed by the coating step after the treatment. As means for achieving the above object of the present invention, the following [1], [2], [3] can be provided. [1] An invention for providing a composition for metal surface treatment characterized by containing (A) a titanium compound and/or a zirconium compound ' and (B) an amino decane (bl) and a polydecyl-functional decane (b 2) Condensation reactants. [2] An invention for a metal surface treatment method comprising the step of contacting a treatment liquid contacting the metal surface treatment liquid containing the metal surface treatment composition according to [1] with a metal material, and subjecting the treatment to the foregoing The water-washing step of the metal material in the liquid contacting step. [3] An invention of a coating method for a metal material, comprising the step of contacting a treatment liquid for contacting a metal surface treatment liquid containing the metal surface treatment composition according to [1] with a metal material, The water washing step of washing the metal material in the treatment liquid contacting step and the coating step of applying the sintering paint (π) on the surface treatment coating layer to be adhered to. Embodiments of the present invention will be described below. 201120245 In the present invention, the titanium compound and/or the zirconium compound (A) is a substance for forming a chemical conversion film containing titanium and/or zirconium on the surface of a metal material, and is to contain the composition of the present invention. When the metal surface treatment liquid is in contact with the metal material, a chemical conversion film containing oxides and/or hydroxides of titanium and/or zirconium may be chromatographed onto the surface of the metal material. The titanium compound and/or the pin compound (A) usually contains at least one compound selected from the group consisting of a halide of titanium and a salt thereof, a halide of cerium and a salt thereof, zirconium carbonate and a salt thereof, and chromium nitrate. It is preferred to contain at least one compound selected from the group consisting of cesium fluoride, titanium fluoride, chromium carbonate and salts thereof, and a nitric acid pin. Specific examples thereof include fluorozirconic acid, sodium chromium fluoride, potassium zirconium fluoride, lithium zirconium fluoride, ammonium zirconium fluoride, zirconium carbonate, zirconium nitrate, fluorotitanic acid, sodium titanium fluoride, and fluorination. Titanium potassium, lithium titanium fluoride, ammonium fluoride fluoride, and the like. Among them, zirconium nitrate, ammonium zirconium fluoride, and ammonium fluoride fluoride are particularly preferable. In the composition of the present invention, the content of the titanium and/or zirconium compound (A) is 5 to 1000 ppm, preferably 20 to 2000 ppm, and more preferably 50 to 500 ppm in terms of metal element, which ensures the metal. The viewpoint of the amount of the film deposited on the surface of the material, as well as economy and the like, is preferable. In the present invention, the condensation reaction product (B) of the amino decane (bl) and the polydecylalkyl functional decane (b2) is used for improving the corrosion resistance of the film, and is improved by the coating step after the treatment. The substance to be formed by the adhesion of the formed coating film can be usually obtained by hydrolyzing an amino decane (bl) and a polydecyl-functional decane (b2) in water, an alcohol or an acidic aqueous solution or the like. 201120245 When hydrolysis is carried out using an acid, for example, hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid or the like can be used. The amino decane (b 1 ) may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane or 3-aminopropylmethyldiethoxydecane. N-phenyl-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 - Aminopropyltriethoxydecane, and the like. The polyalkylene functional decane (b 2) is preferably represented by the following formula (I). (X1 ka-b(R1 )a(R2)bSi-Y-Si(R3)c(R4)d(X2)3.cd ..(1) (In the formula (I), R1, R2, R3 and R4 The hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms is independently represented. Y represents a divalent organic group or an amine. X1 and X2 independently represent a hydrolyzable group. a and b independently represent 0. , 1 or 2, and 0Sa + bS2. c and d independently represent 〇, 1 or 2, and 0 S c + d S 2 .) In the above, R1, R2, R3 and R4 independently represent a hydrogen atom or a carbon atom. a monovalent organic group having a number of 1 to 30. Examples of the monovalent group include a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group; and a functional group such as a hydroxyl group, an epoxy group or an amine group; In the above, Y represents a divalent organic group or an amine. As a divalent organic group, an alkylene alkylene may be mentioned. And an alkylthioether group, or a group containing these groups as a partial structure, and particularly preferably an alkyl group. The number of carbon atoms is 2 to 30, and particularly preferably 2 to 12. In the above, χ1 and χ2 represent a hydrolyzable group. As a hydrolyzable group, The alkoxy group having a carbon number of 1 to 4 is particularly preferably a methoxy group or an ethoxy group. Further, both a + b and c + d are preferably 0 or 1. As the above polyalkylene group functional group Specific examples of the decane (b2) include, for example, bis(trimethoxydecylalkyl)methane, bis(trimethoxydecylalkyl) ethene, and 1,2-di(diethoxy sand-based) acetamidine. 1,2-(trimethoxy sand-based) ethane, bis(triethoxydecyl)hexane, bis(trimethoxydecyl)hexyl, 1,9-di(diethoxy chopped院院)壬院,1,9-二(三methoxy砂院基) brothel, 1,8-two C diethoxy government base) Xinyuan, bis(trimethoxyl) amine, Bis(triethoxydecyl)amine, bis(triethoxydecylmethyl)amine, bis(triethoxydecylpropyl)amine, etc., wherein the safety of the operation is improved and the corrosion resistance of the film is improved. From the viewpoint of improving the adhesion to the coating film, etc., 1,2-bis(triethoxydecylalkyl)ethane is preferred. The ratio of use of the above amino decane (bl) and polydecyl-functional decane (b2) is 50/50 to 99/1, preferably 70/30 to 99/1 in terms of a molar ratio, and further preferably In the range of 80/20 to 95/5, it is preferable from the viewpoints of preventing gelation at the time of production, improving corrosion resistance of the film, economy, and the like. In the present invention, in the production of the condensation reaction product (B), in addition to the above amino decane (bl) and polyalkylene functional decane (b2), organic decane (b3) other than the above may be appropriately added as needed. As such an organic decane (b3), for example, methyltrimethoxydecane 'methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, 2-(3,4 ring) Oxycyclohexyl)ethyltrimethoxydecane, B 201120245 alkenyl trimethoxy decane, vinyl triethoxy decane, p-phenylethylidene trimethoxy decane, 3-methyl propylene methoxy propyl group Dimethoxy oxime' 3-methoxypropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropane Triethoxy decane, 3-propenyloxypropyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyl Trimethoxy decane and the like. From the viewpoint of controlling precipitation, the organodecane (b3) is used in a range that does not impede solubility in a solvent, and is generally 'relative to the total of the amino decane (bl) and the polydecyl-functional decane (b2). The amount of the ear is desirably used in an amount of 100 mol% or less, preferably 50 mol% or less. In the composition of the present invention, the content of the component (B) is preferably from 1 to 5,000 ppm, and preferably from 20 to 500 ppm, in terms of the solid content concentration, from the viewpoint of ensuring the amount of the film and economic efficiency. The composition of the present invention preferably further contains magnesium, zinc, calcium, aluminum, gallium 'indium, copper 'iron, manganese, nickel, from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film. At least one metal element of the group consisting of cobalt, lanthanum, cerium rare earth elements, tin, antimony, bismuth, vanadium, niobium, chromium, molybdenum, tungsten and silver. The supply source of these metal elements is not particularly limited. For example, it may be blended as a nitrate, a sulfate, or a fluoride in a chemical conversion treatment agent. Further, these metal elements may be, for example, in the treatment of iron. Metal ions eluted in the case of a substrate, an aluminum substrate, or a zinc-based substrate. In the composition of the present invention, when the metal element is contained, the content thereof is preferably in the range of from 0.1 to 5,000 ppm in terms of metal element. Among the above-mentioned metal elements, magnesium, aluminum, and the like are preferable, and the content thereof is preferably from 1 to 5,000 ppm, and preferably from 20 to 2,000 ppm, from the viewpoint of improving the adhesion to the coating film and the like. Further, from the viewpoint of improving the corrosion resistance of the film, etc., copper, vanadium or the like is preferable, and the content thereof is suitably in the range of 0.5 to 100 ppm, and preferably 2 to 50 ppm. The composition of the present invention may further contain at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid 'phosphonic acid, hypophosphorous acid, and the like, from the viewpoint of further promoting film formation and improving corrosion resistance of the film. . The content thereof is preferably in the range of from 1 to 50,000 ppm, and more preferably from 5 to 30,000 ppm, based on the solid content. The composition of the present invention may further contain a water-soluble or water-dispersible organic resin from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film. Examples of the water-soluble or water-dispersible organic resin include an epoxy resin, an acrylic resin, a polyester resin, a polyallylamine resin, a polyvinylamine resin, a polybutadiene resin, and a polyurethane. Resin, polyvinyl alcohol, ethylene-vinyl acetate resin, and the like. Further, a melamine resin, a benzoguanamine resin, a urea resin, a (blocked) polyisocyanate, a phenol resin, or the like can be appropriately blended as needed. In the composition of the present invention, when the water-soluble or water-dispersible organic resin is used, the content of the film is improved from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film. It is desirably in the range of 0.1 to 300,000 pprn, and preferably in the range of 5 to 5,000 ppm. 201120245 In order to further improve the stability and precipitation of the composition, the composition of the present invention may contain a surfactant. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Among them, an anionic surfactant, a nonionic surfactant, and preferably Please use these fees. The anionic surfactant may, for example, be a fatty acid salt, an alkyl sulfate salt, an alkylbenzenesulfonate or an alkyl phosphate. The cationic surfactant may, for example, be an alkylamine salt or a quaternary ammonium salt. When a nonionic surfactant is used, the HLB is 8 or more, and preferably in the range of about 10 to about 20. Further, the above HLB represents the equilibrium enthalpy of the hydrophilic group and the lipophilic group in the molecule, and is an abbreviation for Hydrophile-Lipophile Balance. Examples of such a nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether 'polyoxyethylene derivative, sorbitan fatty acid ester, and polyoxyethylene sorbitan fat. An acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene alkylamine, an alkyl alkanolamine or the like. When an anionic surfactant and a nonionic surfactant are used, the anionic surfactant/nonionic surfactant = 99.9/0.1 (% by mass) to 10/based on the total solid content of the two components. 90 (% by mass), and preferably in the range of 80/20 (% by mass) to 50/50 (% by mass). When the above surfactant is used in the composition of the present invention, the content thereof is preferably from 5 to 300,000 ppm, and more preferably from 25 to 300 ppm, from the viewpoint of performing sufficient degreasing treatment, economy, and the like. Within the range of 〇ppm. -12- 201120245 The pH of the composition of the present invention is preferably from 15 to 65, and particularly preferably in the range of from 3 Torr to 4.5. For the adjustment of pH, an acid compound such as nitric acid or sulfuric acid, or a basic compound such as sodium hydroxide, potassium hydroxide or ammonia can be used. In the composition of the present invention, in addition to the above-mentioned components, an optional component may be blended as needed, and examples thereof include cerium oxide such as water-dispersible cerium oxide. The metal surface treatment method of the present invention comprises a step of contacting a treatment liquid containing a metal surface treatment liquid containing the metal surface treatment composition obtained as described above and a metal material, and washing the metal material having passed through the treatment liquid contacting step Washing steps. The treatment liquid contact step is not particularly limited, and for example, a method such as a dipping method, a spray method, or a roll coating method can be employed. Preferably, the temperature of the treatment liquid is adjusted to be in the range of 20 to 70 ° C', particularly 30 to 55 °C. As the metal material, an iron-based substrate, an aluminum-based substrate, a zinc-based substrate, or the like can be usually used. An iron-aluminum and zinc-based substrate means an iron-based substrate formed of iron and/or an alloy thereof, an IS-based substrate formed of aluminum and/or an alloy thereof, and a substrate A zinc-based substrate formed of zinc and/or an alloy thereof. Φ The inventive composition can also be used for a plurality of metal substrates formed of an iron-based substrate, an aluminum-based substrate, and a stomach-based substrate. Chemical conversion treatment of the coating. The method of the present invention is particularly preferably used for an iron-based substrate. The €@metal material is preferably subjected to a fat treatment, a degreasing and water washing treatment, and a water washing step after the treatment liquid contacting step, before the above-mentioned treatment liquid contacting step. -13- 201120245 The above degreasing treatment for removing oil and dirt adhering to the surface of the substrate, and the treatment is a degreasing agent such as a phosphorus-free, nitrogen-free degreasing washing liquid, and usually carried out at 30 to 70 ° C Immersion treatment in seconds to minutes. Pre-degreasing treatment may also be carried out before degreasing treatment as needed. The water washing step after the contact of the above treatment liquid is carried out one or more times in order not to adversely affect the adhesion, corrosion resistance and the like after various coatings. At this time, the final water washing is suitable for pure water. The water washing treatment may be spray water washing or immersion water washing, or these methods may be combined and washed with water. After the above water washing step, a drying step may be employed as needed. When the drying step is carried out, cold air drying can be performed, such as hot air drying. In the film obtained by the method of the present invention, the amount of adhesion to the metal material is preferably from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film, etc., in terms of the metal element contained in the treatment agent. 〇1~2000mg/m2' and particularly preferably 5~200mg/m2. On the film obtained as described above, a conventionally known coating material can be suitably used for coating to form a coating layer ', and an organic resin coating layer may be provided by a binder layer. As the coating material, a conventionally known coating material can be used without particular limitation, and examples thereof include an organic solvent-diluted coating material, an aqueous coating material, and a powder coating material. Further, the 'coating method of the present invention' includes contacting a metal surface treatment liquid containing the composition for metal surface treatment obtained as described above (sometimes referred to as "metal surface treatment composition (1)") with a metal material. Treatment liquid-14-201120245 A contact step, a water washing step of washing the metal material subjected to the treatment liquid contacting step, and a coating step of applying the sintered coating material (II) on the obtained surface treatment coating layer. The treatment liquid contacting step is not particularly limited, and for example, a dipping method such as a spray method or a roll coating method can be employed. Preferably, the temperature of the treatment liquid is adjusted to be in the range of 20 to 70 ° C, particularly 3 to 5 5 °. Examples of the metal material include an iron base material, an aluminum base material, and a zinc base material. The iron, aluminum and zinc-based substrate means that the substrate is an iron-based substrate formed of iron and/or an alloy thereof, the substrate is an is-based substrate formed of aluminum and/or an alloy thereof, and the substrate is A zinc-based substrate formed of zinc and/or an alloy thereof. The metal surface treatment composition (I) can also be used for chemical conversion treatment of a coated object formed of a plurality of metal substrates from an iron substrate, a substrate, and a zinc substrate. The method of the present invention is particularly preferably used for an iron-based substrate. These metal materials are preferably subjected to a 'degreasing water washing treatment" before the above-mentioned treatment liquid contacting step, and a water washing step after the treatment liquid contacting step. ± Degreasing treatment for removing oil and dirt attached to the surface of the substrate. The treatment is a degreasing agent such as a phosphorus-free or nitrogen-free degreasing washing liquid, and is usually carried out at 30 to 70 ° C for several seconds. ~ immersion in a few minutes or so S ° can also be pre-degreased before degreasing treatment as needed. In order to prevent adverse effects such as adhesion and corrosion resistance after various coatings, the water washing step after the contact of the above treatment liquid is performed once or more -15-201120245 times. At this time, the final water washing is suitable for pure water. The water washing treatment may be spray water washing or immersion water washing, and these methods may be combined to perform water washing. After the above water washing step, a drying step may be employed as needed. When the drying step is carried out, cold air drying, hot air drying, or the like can be performed. In the method of the present invention, the amount of the coating obtained by the metal surface treatment composition (1) is increased in the amount of the metal material from the viewpoint of improving the corrosion resistance of the coating film and improving the adhesion to the coating film. The metal element conversion meter is preferably from 0.1 to 2000 mg/m2, and particularly preferably from 5 to 200 mg/m2. In the coating step of the method of the present invention, the sintered coating (II) is applied to the film obtained as described above. As the sintered coating material (II), a conventionally known sintered coating material can be used without any particular limitation, and examples thereof include an organic solvent-diluted coating material, a water-based paint, and a powder coating material. Examples of the organic solvent-diluted coating material include a polyester resin, an alkyd resin, an epoxy resin, an acrylic resin, a urethane resin, a fluororesin, a vinyl chloride resin, and the like, and the like. The base resin component contains, if necessary, an amine-based resin (for example, a melamine resin), a (blocked) polyisocyanate compound, or a polybasic acid which can react with a functional group such as a hydroxyl group or an epoxy group in the matrix resin component. As the coating material of the curing agent, a polyester/melamine resin coating, an alkyd/melamine resin coating, an acrylic coating, or the like can be preferably used. -16- 201120245 In the above organic solvent diluted coating, further compounded with an organic solvent' and, if necessary, appropriately blended with a curing catalyst, a pigment type 'antifoaming agent' coating surface adjusting agent, an anti-settling agent, a pigment dispersing agent, and a fumarin supplement. Additives for coatings such as agents. The organic solvent-diluted coating material can be used for a metal surface treatment composition by a known method such as a roll coating method, a spray coating method, a brush coating method, an electrostatic coating method, a dipping method, a curtain coating method, or a roll coating method (1). The obtained film was coated, and dried to form a coating film. The film thickness of the coating film is not particularly limited, but is usually selected in the range of 3 to 100 #m, and preferably 15 to 50 μm. The drying of the coating film may be appropriately set depending on the type of the resin to be used, etc., but when the material to be coated by a coil coating method or the like is continuously sintered, it is usually at a maximum temperature of 160 to 25 CTC, and preferably. Sintered for 15 to 60 seconds at 180 to 230 ° C. When the sintering is carried out in a batch type, for example, it can be carried out by sintering at a gas atmosphere temperature of 80 to 180 ° C for 5 to 60 minutes. The powder coating material is a coating material which is obtained by melt-kneading a coating composition containing a coating film-forming resin and a coloring pigment or an anthraquinone pigment and other additives which are added as needed, and then pulverizing and pulverizing, and it can be used. The method is manufactured. As the coating film-forming resin, a thermosetting resin or a thermoplastic resin which has been used as a coating film of a powder coating material to form a resin can be used, and the thermosetting resin is generally used. As such a thermosetting resin, for example, (i) a hydroxyl group-containing solid resin and a curing agent having a functional group which undergoes a curing reaction with the hydroxyl group by heat, 5p--17·201120245, (π) a solid resin of a carboxyl group, and a curing agent having a functional group which undergoes a curing reaction with the carboxyl group by heat, (iii) an epoxy group-containing solid resin, and a curing reaction with the epoxy group by heat A combination of functional group curing agents. The "solid" of the resin herein means a solid shape at normal temperature, and preferably has a softening point of 80 to 200 °C. Further, the curing agent may be in a solid form or in a liquid form, and is preferably a substance having a solid shape. As the hydroxyl group-containing solid resin, for example, a known resin for a powder coating material such as a hydroxyl group-containing acryl resin or a hydroxyl group-containing polyester resin can be used. As a "curing agent having a functional group which undergoes a curing reaction with the hydroxyl group by heat", which can be used in combination with the hydroxyl group-containing solid resin, for example, a blocked polyisocyanate compound or an amine-based plastic resin can be used. A curing agent for powder coatings. As the carboxyl group-containing solid resin, for example, a carboxyl group-containing acrylic resin or a carboxyl group-containing polyester resin known as a resin for a powder coating can be used. As a "curing agent having a functional group which undergoes a curing reaction with the carboxyl group by heat", which can be used in combination with the carboxyl group-containing solid resin, for example, bisphenol.A to epichlorohydrin type epoxy resin or fat can be used. A known epoxy resin, a novolac type epoxy resin, an epoxy resin such as an epoxy group-containing acrylic resin, or a known curing agent for a powder coating material such as a hydroxyalkylguanamine compound. Further, as the epoxy group-containing solid resin, for example, a bisphenol A to epichlorohydrin epoxy resin alicyclic epoxy resin, a novolak epoxy resin, an epoxy group-containing acrylic resin, or the like can be used. A resin for powder coatings. As a "curing agent having a functional group which undergoes a curing reaction with the epoxy group by heat" used in combination with the epoxy resin containing an epoxy-18 - 201120245 group, for example, a carboxyl group-containing polyester resin can be used. A known curing agent for a powder coating material such as an organic acid polyfluorene compound, an imidazole compound, a dicyandiamide compound, a polycarboxylic acid compound, or an acid anhydride. In view of the fact that the corrosion resistance of the coating film is good even if the sintering temperature is low, a combination of a carboxyl group-containing polyester resin and a hydroxyalkylguanamine compound is particularly preferable. The powder coating material can be applied to a film obtained from the metal surface treatment composition (I) by a known method such as an electrostatic coating method, a flow dipping method, a spray coating method or an in-mold decoration method, and a hot air furnace can be used. The infrared furnace, the induction heating furnace, and the like are sintered to form a cured coating film. The film thickness of the coating film to be formed is a film thickness after sintering, and is usually in the range of 30 to 250 #m, and preferably 40 to 150 #m. The sintering condition of the powder coating material is preferably carried out at a temperature of 130 to 350 ° C, preferably 140 to 250 ° C, for a period of 30 to 60 minutes, and preferably 1 to 50. minute. In the present invention, even when a coating material having a high shrinkage stress of a cured coating film is used in the above coating material, the adhesion of the coating film is excellent. Further, the coated metal sheet obtained as described above may have a structure in which a coating film is formed only from the above-mentioned coating material, and may have a multilayer structure in which a top coat coating film is further appropriately formed. Advantageous Effects of Invention According to the metal surface treatment composition and the metal surface treatment method of the present invention, chromic acid can be obtained by including a specific 矽-19-201120245 alkane condensation reaction product in a surface treatment agent of zirconium or titanium. The salt treatment or the phosphate treatment is equivalent to the corrosion resistance, and it is possible to form a film which is excellent in adhesion to the coating film formed by the coating step after the treatment. Further, according to the coating method of the present invention, by providing a surface treatment agent of zirconium or titanium type with a specific decane condensation reaction product, the obtained surface treatment film can be obtained as resistant to chromate treatment or phosphate treatment. It is also highly corrosive and has excellent adhesion to the coating film formed by the coating step after the treatment. In particular, when a sintered paint having a large shrinkage stress in the coating film during sintering is used, adhesion to the coating film does not occur. Therefore, the coating method of the present invention is very useful for industrial coating applications such as home appliances and steel furniture. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples. In addition, "parts" and "%" mean "parts by mass" and "mass %" unless otherwise stated. Production of decane condensation reaction product (B) Production Example 1 In a 1 L round bottom flask equipped with a reflux condenser, a thermometer, a nitrogen gas introduction tube, and a stirrer, 200 g of isopropyl alcohol and 200 g of deionized water were placed, and the mixture was stirred. Nitrogen gas was introduced into the gas phase, and while stirring, 90 g of 3-aminopropyltrimethoxydecane and 1 g of di(triethoxydecylalkyl)ethane were added in one portion. After stirring at room temperature for 1 hour, the reaction was carried out at 60 ° C for 6 hours, and after -20-201120245, the fraction was removed, and while being exchanged with propylene glycol monomethyl ether, the temperature was raised to a boiling point of 120 °C. After cooling to 60 ° C, the mixture was concentrated by vacuum distillation to obtain a solution of 120 g of a product (P1) having a nonvolatile content of 40%. The resulting product (P1) had a nonvolatile content of 40% solution and was a colorless, transparent, viscous liquid. Production Example 2 to 1 2 In the same manner as in Production Example 1, except that the raw material composition was as shown in Table 1, each of the products (P1) to (P8) and (R1) to (R4) were obtained. 201120245 π嗽] s § 200 200 m Pi 200 200 Cn pcJ \Ti m inch W 200 200 5 o 200 200 OO o 〇200 200 cu g 卜r〇200 200 VO (X ir> 〇ΓΛ inch 200 200 Pu l〇 200 200 Z 200 200 m CL, 200 200 CN Oh in 200 200 5: ο 200 200 m « Reduced secret · 53⁄4 fO fr ^ 111 111 s _ tide ggf K: E f 9 f狴 ΰ gfii E , Π Ml « «1 « _ _ us 宁tt _ <7 _ _ ss thin disk rji c|) _ rA rA ZZZ ga ^ E: « m fr El· secret K) l· III HI 's—✓ 'w^ 11 11 遁嫲Ε ΠΙ m h0 1 S 1 m W l|f fr酹ni 4 Slightly d: E* CN Isopropanol deionized hydrocarbyl decane (bl) Polyalkylene functional decane (b2) Organic decane (b3) 201120245 Examples 1 to 26 and Comparative Examples 1 to 4 Preparation of Metal Surface Treatment Compositions In the above-mentioned (P1) to (P8) and (R1) to (R4), fluorozirconic acid, fluorotitanic acid, and nitrates of various metals were used. The composition for metal surface treatment having the composition shown in Table 2 was adjusted. In Table 2, the concentration of each metal component is expressed in terms of a metal element, and the other component concentrations indicate the solid content concentration. Chemical conversion treatment and coating are commercially available cold-rolled steel sheets (SPCC-SD, manufactured by Test Panel, Japan, 70mmxl50mmx0.8mm), galvanized steel sheets (GA steel sheets, manufactured by Japan Test Panel, 70mmxl50mmx0.8mm), 5000 series Jin (made by Japan Test Panel, 70mmxl50mmx0.8mm) or 6000 Department Ming (Japan Ding 63 〖? 31^1 company manufacturing, 7〇111111\15〇111111 <0.8111111) As the substrate, the chemical conversion treatment under the conditions (1) to (4) and Table 3 shown below was carried out. (1) The base material was immersed in a commercially available degreased liquid adjusted to 40 °C for 2 minutes, degreased, and then subjected to a water washing treatment for 30 seconds using tap water. (2) Next, the water-washed metal substrate was immersed for 10 to 300 seconds at the metal surface of each of the examples and the comparative examples adjusted to pH and temperature as shown in Table 3. . The pH was adjusted to 3.2 to 4.2 using nitric acid or sodium hydroxide. Also, adjust the temperature to 35~50 °C. (3) Each of the substrates after the above treatment was washed with tap water for 30 seconds, and then water-washed for 30 seconds with ion-exchanged water. Then, it was dried at 80 °C for 5 minutes using a hot air drying oven to form each chemical conversion processing plate. 0-23-201120245 The processing of each chemical conversion processing plate was performed using "XRF1700" (a fluorescent X-ray analyzer manufactured by Shimadzu Corporation). The amount of film was analyzed as a total amount of attached metal. The results are shown in Table 4. (4) Gas spray coating was performed on each of the chemical conversion treatment plates obtained above to make the dry film thickness of "Akabe RIZE" (aqueous polyester polyurethane-based sintered coating) 30 / / m, and sintering was performed by heating at 150 ° C for 30 minutes to prepare each test coated board. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 4. Further, (Note 1) to (Note 3) in Table 2 are as follows. (Note 1) Organic resin: "PAA25", trade name, manufactured by Nitto Bose Co., Ltd., aqueous solution of polyallylamine resin (Note 2) Surfactant: "N ewc ο 1 1 1 0 0 ", trade name, Manufactured by Japan Emulsifier Co., Ltd., nonionic surfactant (Note 3) cerium oxide: "Snowtex 0", trade name, manufactured by Nissan Chemical Industry Co., Ltd., water dispersible (colloidal) silica sand comparative example 5 Gas spray coating on a commercially available zinc phosphate chemical conversion treated steel sheet (substrate: SPCC-SD' manufactured by TestPanel Co., Ltd.) to make "Akabe RIZE" (aqueous polyester urethane) The sintered coating material had a dry film thickness of 30/zm and was sintered at 150 ° C for 30 minutes to prepare a test coated plate. The obtained test coated panels were supplied to the following evaluation test. The results are shown in Table 4. -24-201120245 Comparative Example 6 A test was carried out in the same manner as in Comparative Example 5 except that a commercially available zinc phosphate-based chemical conversion-treated steel sheet (base material: GA steel sheet, manufactured by Test Panel, Japan) was used in Comparative Example 5'. Coating board. The obtained test coated panels were supplied to the evaluation test described below. The results are shown in Table 4. Comparative Example 7 A test coating plate was produced in the same manner as in Comparative Example 5 except that a commercially available chromate-based chemical conversion-treated steel sheet (base material: 5000-series aluminum, manufactured by Japan Test Panel Co., Ltd.) was used. . The resulting test coated panels were supplied to the evaluation test described below. The results are shown in Table 4. Evaluation test (*1) Corrosion resistance: For each test coated board, a cross-cut cut deep to the base was cut on the coating film with a knife to carry out a salt spray corrosion test (SST: according to JIS Z-2371. It was 35 ° C for 240 hours, and then the adhesive portion was used to bond and peel the wound portion, and the peeling width of the coating film was measured. The evaluation criteria are as follows. ◎: Unpeeled 〇: The peeling width is within 3 mm Δ: The peeling width exceeds 3 mm and is within 5 mm X: The peeling width exceeds 5 mm » (* 2) (after water resistance) Adhesion: Each test plate is coated in warm water (40 After immersing for 240 hours in °C), the cutting marks (10x10, 1 mm interval) were cut out on the cutting board immediately after the removal, and the adhesive tape was used for bonding and peeling, and the number of peeling marks of the coating film was checked. The evaluation criteria are as follows. -25- 201120245 ◎: No peeling grid: The stripping grid is less than 5 △: The stripping grid is 6~1 0 X: The stripping grid is 1 1 or more -26- 20 4502 2 u«] ym δ铽S surfactant (Note 1) (100) polar resin (Note 2) (50) cerium oxide (Note 3) (100) _ surfactant (Note 1) (100) mmm 1 (including ffipprn) nitric acid Οοοο) S' § m Nitric acid (2000) Nitric acid (2000) Nitric acid (2000) S' ο CS i Nitric acid (2000) 1 Μ m Nitric acid (2000) Sulfuric acid (5000) Niobium nitric acid (1000) Nitric acid (1000) Nitric acid (5000 Nitric acid (i oooo) 硝酸 Nitric acid (_〇) Phosphoric acid (20) Nitric acid (5000) Nitric acid (5000) Nitric acid (ιοοοο)! Nitric acid (10000) Nitric acid (5000) 1 --! Nitric acid (5 〇〇〇) Nitric acid (5000) Nitric acid (5000> hypophosphorous acid (25) nitric acid (10000) § im Mo L. !- ! 300 U cS CO •Λ > *Λ 〇> «Λ Λ «Λ m 3 w *n <n 2 i ο ο 5 »ri m 6 o < 〇ο s 〇c3 «Λ N 200 1000 -1 500 ! «) 500 2000 500 500 500 Brothel Condensation Reactant (in ppm) ο CU 1 CU P3(l〇〇) 2 ι/i CU 1 〇 4 Ρ7(100) s Μ gca PI(100) 〇£ cc 0k Pl(100) ! E gs 1 eu cm CU Pl(50) I | PH200) P4(100) ! £ Η 1 200 ο !00 300 Ν ο ο 200 400 ο 100 o O 200 300 400 )00 200 ο 100 〇200 200 — <sr·* »a· •ο Ό r* 00 9> o 2 2 ΤΓ «η «ο 00 〇 \ μ -Z(N_一-i·- 201120245 Nitric acid (2000) Nitric acid (2000) Nitric acid (5000 Nitric acid (3000) Nitric acid (5000) Nitric acid (5000) W-) 〇Ό jq 1000 1 1000 c S eu s 2 2 S g 〇o ο § 〇IQ — ΓΝ
-8CNI ~.& 201120245 [表3] 金屬基材 PH 時間(秒） 溫度(。〇 1 冷軋鋼板 3.5 30 40 2 冷軋鋼板 4 60 40 3 冷軋鋼板 4 180 40 4 冷軋鋼板 4 120 35 5 冷軋鋼板 4.2 120 40 6 冷軋鋼板 4 120 40 7 冷軋鋼板 4 120 35 8 冷軋鋼板 3.8 180 40 9 冷軋鋼板 3.8 120 40 10 冷軋鋼板 3.5 60 40 11 冷乳鋼板 4 60 50 12 冷軋鋼板 4 120 40 實施例 13 冷軋鋼板 4 10 40 14 5000系鋁 3 30 50 15 冷軋鋼板 4 120 35 16 冷軋鋼板 4 60 40 17 冷軋鋼板 4 120 35 18 冷軋鋼板 4 120 50 19 6000系鋁 3.2 120 50 20 冷軋鋼板 4 60 40 21 冷軋鋼板 3.8 30 40 22 冷軋鋼板 4 60 40 23 冷軋鋼板 4.2 . 60 40 24 冷乳鋼板 3.5 60 40 25 冷軋鋼板 4 60 40 26 鍍鋅類鋼板 3.8 25 35 1 冷軋鋼板 4 120 40 比較例 2 冷軋鋼板 4 120 40 3 冷軋鋼板 4 120 40 4 冷軋鋼板 4 120 40 201120245 [表4] 金屬皮膜量(mg/m2) 耐腐蝕性 附著性 1 21 ◎ ◎ 2 33 ◎ ◎ 3 41 ◎ ◎ 4 40 ◎ ◎ 5 29 ◎ ◎ 6 41 ◎ ◎ 7 33 ◎ ◎ 8 51 ◎ ◎ 9 48 ◎ ◎ 10 22 ◎ ◎ 11 27 ◎ ◎ 12 52 ◎ ◎ 實施例 13 16 ◎ ◎ 14 25 ◎ ◎ 15 39 ◎ ◎ 16 28 ◎ ◎ 17 36 ◎ ◎ 18 62 ◎ ◎ 19 13 ◎ ◎ 20 34 ◎ ◎ 21 19 ◎ ◎ 22 31 ◎ ◎ 23 37 ◎ ◎ 24 43 ◎ ◎ 25 24 ◎ ◎ 26 14 ◎ ◎ 1 54 Δ Δ 2 51 Δ X 3 37 Δ Δ 比較例 4 29 X X 5 2300 〇 ◎ 6 3200 〇 〇 7 11 〇 ◎ -30- 201120245 實施例27〜52以及比較例8〜1 1 金屬表面處理用組成物的製作 在上述製作的（P1)〜（P8)以及（R1)〜（R4)中，使用氟锆 酸 '氟鈦酸以及各金屬的硝酸鹽等，調整具有表5所示組 成的金屬表面處理用組成物。在表5中，各金屬成分的濃 度以金屬元素換算進行表示，除此之外的成分濃度表示固 體成分濃度。此外，表5中的（註1)〜（註3)如下所述。 (註1)有機樹脂：“ PAA25” ，商品名，日東紡股份有 限公司製造，聚烯丙基胺樹脂水溶液 (註2)界面活性劑：“ Newcol 1 100” ，商品名，日本乳 化劑股份有限公司製造，非離子類界面活性劑 (註 3)二氧化矽：“Snowtex 0” ，商品名，日產化學 工業股份有限公司製造，水分散性（膠態）二氧化矽 化學轉換處理 以市售的冷軋鋼板（SPCC-SD，日本Test Panel公司製 造，70mmxl50mmx0.8mm)、鍍鋅類鋼板（GA鋼板，日本Test Panel 公司製造，70mmxl50mmx0.8mm)、5000 系銘（日本 Test Panel 公司製造，70mmxl50mmx0.8mm)或 6000 系銘（日本 丁651?&1^1公司製造，7〇111111><15〇111111><0.8111111)作爲基材，進行 下述所示的步驟以及表5條件下的化學轉換處理。 (1)將上述基材在調整至4 0 °C的市售脫脂液中浸漬2分 鐘，進行脫脂處理後，使用自來水進行3 0秒鐘水洗處理。 -3 1- 201120245 (2) 接著，將水洗後的金屬基材，在調整至表6所示的 pH和溫度的各實施例和比較例的金屬表面處理用組成物 中浸漬處理10〜300秒鐘。使用硝酸或氫氧化鈉將pH調整 至3.2〜4.2。並且，將溫度調整至35〜50°C。 (3) 使用自來水對上述處琿後的各基材進行30秒鐘水 洗後，再用離子交換水進行30秒鐘水洗處理。接著，使用 熱風乾燥爐，在80°C下乾燥5分鐘，形成各化學轉換處理 板。 使用“ XRF1 700” （島津製作所製造，螢光X線分析裝 置），把各化學轉換處理板的處理皮膜量當作附著金屬的合 計量進行分析。結果示於表6。 試驗塗裝板（1)的製作 在上述所得的各化學轉換處理板上進行氣體噴霧塗 裝，使“ Magicron#1000” （關西油漆公司製造，丙燦酸/蜜 胺樹脂類有機溶劑稀釋型塗料）的乾燥膜厚爲30 em，並在 160°C下加熱30分鐘進行燒結，製作各試驗塗裝板。將所 得的各試驗塗裝板提供至下述評價試驗。結果示於表6。 試驗塗裝板（2)的製作 在上述所得的各化學轉換處理板上進行氣體噴霧塗 裝’使“Amilac#1 000” （關西油漆公司製造，醇酸/蜜胺樹 脂類有機溶劑稀釋型塗料）的乾燥膜厚爲30μ m，並在130 °C下加熱30分鐘進行燒結，製作各試驗塗裝板。將所得的 各試驗塗裝板提供至下述評價試驗。結果一倂示於表6。 試驗塗裝板（3)的製作 -32- 201120245 在上述所得的各化學轉換處理板上進行氣體噴霧塗 裝’使“ ASIME”（關西油漆公司製造，聚酯/蜜胺樹脂類有 機溶劑稀釋型塗料）的乾燥膜厚爲30 Am，並在14CTC下加 熱30分鐘進行燒結，製作各試驗塗裝板。將所得的各試驗 塗裝板提供至下述評價試驗。結果一倂示於表6。 試驗塗裝板（4)的製作 在上述所得的各化學轉換處理板上進行靜電粉體塗 裝，使“EvaClad8900” （關西油漆公司製造，含有含羧基的 聚酯樹脂/羥烷基醯胺化合物的粉體塗料）的乾燥膜厚爲 60以m，並在150°C下加熱30分鐘進行燒結，製作各試驗 塗裝板。將所得的各試驗塗裝板提供至下述評價試驗。結 果一倂示於表6。 試驗塗裝板（5)的製作 在上述所得的各化學轉換處理板上進行靜電粉體塗 裝，使“ Evaclad4900”（關西油漆公司製造，含有羥基的聚 酯樹脂/封端化的聚異氰酸酯化合物的粉體塗料）的乾燥膜 厚爲70 m，並在180°C下加熱30分鐘進行燒結，製作各 試驗塗裝板。將所得的各試驗塗裝板提供至下述評價試 驗。結果一倂示於表6。 比較例1 2 除了使用市售的磷酸鋅類化學轉換處理鋼板（基材： SPCC-SD »日本Test Panel公司製造）外，和實施例27〜52 以及比較例8〜11同樣進行各自塗裝，製作各試驗塗裝板。 -33- 201120245 將所得的各試驗塗裝板提供至下述評價試驗。結果一倂示 於表6。 比較例1 3 除了使用市售的磷酸鋅類化學轉換處理鋼板（基材：ga 鋼板，日本Test Panel公司製造）外’和實施例27〜52以及 比較例8〜11同樣進行各自塗裝，製作各試驗塗裝板。將 所得的各試驗塗裝板提供至下述評價試驗。結果一倂結果 一併示於表6。 比較例1 4 除了使用市售的鉻酸鹽類化學轉換處理板（基材：5000 類鋁，曰本TestPanel公司製造）外，和實施例27〜52以及 比較例8〜11同樣進行各自塗裝，製作各試驗塗裝板。將 所得的各試驗塗裝板提供至下述評價試驗。結果一倂示於 表6。 評價試驗 (* 1)耐腐蝕性：對於各實施例和比較例的試驗塗裝板 (1)〜（3)，用刀在塗膜上切出深至基底的十字割痕，使其進 行鹽水噴霧腐蝕試驗（SST:根據JISZ— 2371。鹽水溫度爲 3 5 °C ) 240小時，然後使用黏合帶對刀傷部分進行黏合、剝 離’測定塗膜的剝離寬度。並且，對於各實施例和比較例 的試驗塗裝板（4)〜（5)，用刀在塗膜上切出深至基底的十字 割痕’使其進行鹽水噴霧腐蝕試驗（SST:根據ns Z — 2371。 鹽水溫度爲35 °C )480小時，然後使用黏合帶對刀傷部分進 行黏合、剝離’測定塗膜的剝離寬度。評價基準如下所述^ -34- 201120245 ◎:未剝離 〇：剝離寬度在3mm以內 △:剝離寬度超過3mm並在5mm以內 X:剝離寬度超過5mn^ (* 2)(耐水後）附著性：將各實施例和比較例的試驗塗 裝板（1)〜（5 )在溫水（4 0 °C )中浸漬2 4 0小時，撈出後立刻在 其上切出棋盤格狀（10x10個，間隔爲1mm)的割痕，使用黏 合帶進行黏合、剝離，檢査塗膜的剝離格個數。評價基準 如下所述。 ◎:無剝離格 〇：剝離格爲5個以內 △:剝離格爲6〜10個 X :剝離格爲1 1個以上 -35- 201120245 -5 1 § 〇 ο o W) r^t 〇 〇 m ΟΙ 〇 Ο 〇 〇 〇 w*i ο »η 〇 ο 時間(秒） I ο s 120 % § S 1 120 § ο § g s 120 120 1 120 180 ; S S a «Λ 々 μ 'Τ 00 r*i 90 fW «1 r*i »r 00 «T eo ΓΊ· Q. s 筠 m 崗 铥 j 其他成份 (含 ffl： Ppm) £ M s 有機樹脂(註2)(50) δ 11 界面活性劑(註1)(100) 酸麵 (含进ppm) Ο r·» Μ 程 f ο i m 硝酸(30Q0> 硝酸(3000) 硝酸(3000) 硝酸(3000) 硝酸(3000) ο r··» g m 硝酸(3000) 硫酸(5000) 硝酸(1000) 硝酸(1000) 硝酸(5000) 〇 i 硝酸(10000) 磷酸(20) 硝酸(5000) 硝酸(5000) ο Μ 痤 硝酸(10000) 硝酸(5000) S' i & m 硝酸(5000) ΰ a CQ «Λ > m ο ΪΗ «Λ S 3 V3 ο g 沄 1 〇 V lx. ο a ο *Λ «〇 c s ο < Ο o W*1 200 1000 § 1000 2000 500 500 矽院縮合 反應物 (含S ppm〕 Μ £ s a. s 2 | 2 S 〇 Cl. i s PI(100) £ S ε Pl(100) s g ! S a. 邑 ε S CS Έ Η 100 200 100 300 Ν ο o 200 Ο O 400 ο 〇 200 »Λ g ο 200 ο 100 金晒材料 冷軋網板 冷軋鋼板 冷軋辋板 冷軋鋼板 冷軋鋼板 冷軋鋼板 冷軋鋼板 冷軋綱板 冷軋鋼板 冷軋鋼板 1 1冷軋鋼扳 冷軋鋼板 5000系鋁 冷軋鋼板 1 1 冷軋網板1 冷軋鋼板 I冷軋鋼板 6000系鋁 冷軋鋼板 冷軋鋼板 Q〇 a Ρί η *〇 VO η 00 η 〇\ ο Μ 5 ο m 丨 9 ε -Ml 201120245 ο ο ο O «Λ Γ"ί 〇 〇 〇 β ο s 沄 § ν> fS 120 120 120 S w> fn 00 DO C0 硝酸(5000) 次磷酸Ρ5) 硝酸(10000} S' 0 1 m 硝酸(2000) 硝酸(2000) I Μ 闺 硝酸(2000) 硝酸(5000) 硝酸(5000> ο «Λ 200 沄 W-l rs 〇 1000 500 300 500 P4(100) 1 1 ε S § a m 2 勝 ο 〇 O 200 O Ο 200 200 200 冷軋鋼板 冷軋鋼板 冷軋鋼板 冷軋鋼板 鍍粹類鋼板 冷軋綱板 冷眺鋼板 冷軋鋼板 冷軋鋼板 CO λ «0 〇 二 丨卜ε_¾. .201120245 [表6] 金屬皮 膜量 (mg/m2) 試驗塗板⑴ 試驗塗板 (2) 試驗塗板 (3) 試驗 塗板 試驗塗板 (5) 耐腐 附著 耐腐 附著 耐腐 附著 耐腐 附著 耐腐 附著 蝕性 性 蝕性 性 蝕性 性 蝕性 性 蝕性 性 27 57 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 28 45 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 29 26 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 30 21 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 31 46 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 32 23 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 33 41 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 34 37 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 35 61 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 36 63 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 37 16 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 實 施 例 38 52 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 39 29 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 40 22 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 41 24 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 42 53 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 43 37 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 44 67 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 45 29 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 46 42 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 47 34 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 48 58 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 49 66 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 50 31 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 51 26 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 52 13 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 8 56 Δ 〇 Δ 〇 Δ Δ X 〇 Δ Δ 9 64 Δ Δ Δ Δ Δ X X 〇 Δ Δ 比 10 43 Δ Δ Δ △ Δ Δ X 〇 Δ Δ 較 11 21 X Δ X X X X X 〇 X Δ 例 12 2300 〇 ◎ 〇 ◎ 〇 〇 〇 Δ 〇 ◎ 13 3200 ◎ ◎ ◎ ◎ ◎ 〇 〇 Δ ◎ ◎. 14 11 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ -38- S-·-8CNI ~.& 201120245 [Table 3] Metal substrate PH time (seconds) Temperature (.〇1 Cold rolled steel sheet 3.5 30 40 2 Cold rolled steel sheet 4 60 40 3 Cold rolled steel sheet 4 180 40 4 Cold rolled steel sheet 4 120 35 5 Cold rolled steel plate 4.2 120 40 6 Cold rolled steel plate 4 120 40 7 Cold rolled steel plate 4 120 35 8 Cold rolled steel plate 3.8 180 40 9 Cold rolled steel plate 3.8 120 40 10 Cold rolled steel plate 3.5 60 40 11 Cold milk steel plate 4 60 50 12 Cold rolled steel plate 4 120 40 Example 13 Cold rolled steel plate 4 10 40 14 5000 series aluminum 3 30 50 15 Cold rolled steel plate 4 120 35 16 Cold rolled steel plate 4 60 40 17 Cold rolled steel plate 4 120 35 18 Cold rolled steel plate 4 120 50 19 6000 series aluminum 3.2 120 50 20 cold rolled steel plate 4 60 40 21 cold rolled steel plate 3.8 30 40 22 cold rolled steel plate 4 60 40 23 cold rolled steel plate 4.2 . 60 40 24 cold milk steel plate 3.5 60 40 25 cold rolled steel plate 4 60 40 26 Galvanized steel plate 3.8 25 35 1 Cold rolled steel plate 4 120 40 Comparative example 2 Cold rolled steel plate 4 120 40 3 Cold rolled steel plate 4 120 40 4 Cold rolled steel plate 4 120 40 201120245 [Table 4] Metal film amount (mg/ M2) Corrosion resistance Adhesion 1 21 ◎ ◎ 2 33 ◎ ◎ 3 41 ◎ 4 40 ◎ ◎ 5 29 ◎ ◎ 6 41 ◎ ◎ 7 33 ◎ ◎ 8 51 ◎ ◎ 9 48 ◎ ◎ 10 22 ◎ ◎ 11 27 ◎ ◎ 12 52 ◎ ◎ Example 13 16 ◎ ◎ 14 25 ◎ ◎ 15 39 ◎ ◎ 16 28 ◎ ◎ 17 36 ◎ ◎ 18 62 ◎ ◎ 19 13 ◎ ◎ 20 34 ◎ ◎ 21 19 ◎ ◎ 22 31 ◎ ◎ 23 37 ◎ ◎ 24 43 ◎ ◎ 25 24 ◎ ◎ 26 14 ◎ ◎ 1 54 Δ Δ 2 51 Δ X 3 37 Δ Δ Comparative Example 4 29 XX 5 2300 〇 ◎ 6 3200 〇〇 7 11 〇 ◎ -30- 201120245 Examples 27 to 52 and Comparative Examples 8 to 1 1 Preparation of a composition for metal surface treatment was carried out as described above In the (P1) to (P8) and (R1) to (R4), the composition for metal surface treatment having the composition shown in Table 5 was adjusted using fluorozirconic acid 'fluorotitanic acid and a nitrate of each metal. In Table 5, the concentration of each metal component is expressed in terms of a metal element, and the other component concentrations indicate the solid content concentration. Further, (Note 1) to (Note 3) in Table 5 are as follows. (Note 1) Organic resin: "PAA25", trade name, manufactured by Ridong Textile Co., Ltd., polyallylamine resin aqueous solution (Note 2) Surfactant: "Newcol 1 100", trade name, Japanese emulsifier limited stock Made by the company, non-ionic surfactant (Note 3) cerium oxide: "Snowtex 0", trade name, manufactured by Nissan Chemical Industry Co., Ltd., water-dispersible (colloidal) cerium oxide chemical conversion treatment is commercially available Cold-rolled steel sheet (SPCC-SD, manufactured by Test Panel, Japan, 70mmxl50mmx0.8mm), galvanized steel sheet (GA steel sheet, manufactured by Japan Test Panel, 70mmxl50mmx0.8mm), 5000 series (manufactured by Japan Test Panel, 70mmxl50mmx0. 8mm) or 6000 series (manufactured by Nippon Ding 651? & 1^1, 7〇111111><15〇111111><0.8111111) as a substrate, and the following steps and conditions under Table 5 were carried out. Chemical conversion treatment. (1) The base material was immersed in a commercially available degreased liquid adjusted to 40 ° C for 2 minutes, degreased, and then subjected to a water washing treatment for 30 seconds using tap water. -3 1-201120245 (2) Next, the metal substrate after washing was immersed for 10 to 300 seconds in the metal surface treatment composition of each of the examples and the comparative examples adjusted to the pH and temperature shown in Table 6. bell. The pH was adjusted to 3.2 to 4.2 using nitric acid or sodium hydroxide. Also, the temperature was adjusted to 35 to 50 °C. (3) Each of the substrates after the above treatment was washed with tap water for 30 seconds, and then washed with ion-exchanged water for 30 seconds. Subsequently, it was dried at 80 ° C for 5 minutes using a hot air drying oven to form each chemical conversion treatment plate. The "XRF1 700" (manufactured by Shimadzu Corporation, a fluorescent X-ray analysis apparatus) was used to analyze the amount of the treated film of each chemical conversion treatment plate as a total amount of the attached metal. The results are shown in Table 6. Preparation of the test coated board (1) Gas spray coating was carried out on each of the chemical conversion treatment plates obtained above to make "Magicron #1000" (manufactured by Kansai Paint Co., Ltd., a polyacrylic acid/melamine resin type organic solvent diluted type coating) The dried film thickness was 30 em, and it was sintered by heating at 160 ° C for 30 minutes to prepare each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Preparation of Test Coating Plate (2) Gas spray coating was performed on each of the chemical conversion treatment plates obtained above to make "Amilac #1 000" (manufactured by Kansai Paint Co., Ltd., alkyd/melamine resin type organic solvent diluted coating) The dried film thickness was 30 μm, and it was sintered by heating at 130 ° C for 30 minutes to prepare each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Production of test coated board (3) -32- 201120245 Gas spray coating on each of the chemical conversion treatment plates obtained above - "ASIME" (manufactured by Kansai Paint Co., Ltd., polyester/melamine resin type organic solvent diluted type) The coating film had a dry film thickness of 30 Am and was sintered by heating at 14 CTC for 30 minutes to prepare each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Preparation of Test Coating Plate (4) Electrostatic powder coating was carried out on each of the chemical conversion treatment plates obtained above, and "EvaClad 8900" (manufactured by Kansai Paint Co., Ltd., containing a carboxyl group-containing polyester resin/hydroxyalkylguanamine compound) The powder coating material had a dry film thickness of 60 m and was heated at 150 ° C for 30 minutes to be sintered to prepare each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Preparation of Test Coating Plate (5) Electrostatic powder coating was carried out on each of the chemical conversion treatment plates obtained above, and "Evaclad 4900" (manufactured by Kansai Paint Co., Ltd., a hydroxyl group-containing polyester resin / blocked polyisocyanate compound) The powder coating) had a dry film thickness of 70 m and was sintered by heating at 180 ° C for 30 minutes to prepare each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Comparative Example 1 2 Each of the coatings was carried out in the same manner as in Examples 27 to 52 and Comparative Examples 8 to 11 except that a commercially available zinc phosphate-based chemical conversion-treated steel sheet (base material: SPCC-SD » manufactured by Japan Test Panel Co., Ltd.) was used. Each test coated plate was produced. -33- 201120245 Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Comparative Example 1 3 Each of the coatings was produced in the same manner as in Examples 27 to 52 and Comparative Examples 8 to 11 except that a commercially available zinc phosphate-based chemical conversion-treated steel sheet (base material: ga steel sheet, manufactured by Japan Test Panel Co., Ltd.) was used. Each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Comparative Example 1 4 Each of the coatings was carried out in the same manner as in Examples 27 to 52 and Comparative Examples 8 to 11 except that a commercially available chromate-based chemical conversion treatment plate (substrate: 5000 type aluminum, manufactured by Sigma TestPanel Co., Ltd.) was used. , each test coating plate was produced. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6. Evaluation test (*1) Corrosion resistance: For the test coated sheets (1) to (3) of the respective examples and comparative examples, a cross cut deep to the base was cut on the coating film with a knife to carry out salt water. The spray corrosion test (SST: according to JIS Z-2371. The brine temperature was 35 ° C) for 240 hours, and then the adhesive tape was used to bond and peel the blade portion to determine the peeling width of the coating film. Further, with respect to the test-coated sheets (4) to (5) of the respective examples and comparative examples, the cross-cuts of the base were cut out on the coating film by a knife to perform a salt spray corrosion test (SST: according to ns Z — 2371. The temperature of the brine is 35 ° C for 480 hours, and then the adhesive tape is used to bond and peel the portion of the knife to determine the peeling width of the coating film. Evaluation criteria are as follows: ^ -34- 201120245 ◎: Unpeeled 〇: peeling width is within 3 mm △: peeling width exceeds 3 mm and is within 5 mm X: peeling width exceeds 5 mn^ (* 2) (after water resistance) Adhesion: The test coated plates (1) to (5) of the respective examples and comparative examples were immersed in warm water (40 ° C) for 270 hours, and immediately after the removal, a checkerboard shape (10 x 10 pieces) was cut out thereon. For the cuts with a spacing of 1 mm, the adhesive tape is used for bonding and peeling, and the number of peeling marks of the coating film is checked. The evaluation criteria are as follows. ◎: No peeling grid: The stripping grid is 5 or less Δ: The stripping grid is 6 to 10 X: The stripping grid is 1 1 or more -35- 201120245 -5 1 § 〇ο o W) r^t 〇〇m ΟΙ 〇Ο 〇〇〇w*i ο »η 〇ο Time (seconds) I ο s 120 % § S 1 120 § ο § gs 120 120 1 120 180 ; SS a «Λ 々μ 'Τ 00 r*i 90 fW «1 r*i »r 00 «T eo ΓΊ· Q. s 筠m Gang j j Other ingredients (including ffl: Ppm) £ M s Organic resin (Note 2) (50) δ 11 Surfactant (Note 1 ) (100) Acid surface (in ppm) Ο r·» f f ο im Nitric acid (30Q0> Nitric acid (3000) Nitric acid (3000) Nitric acid (3000) Nitric acid (3000) ο r··» gm Nitric acid (3000) Sulfuric acid (5000) Nitric acid (1000) Nitric acid (1000) Nitric acid (5000) 〇i Nitric acid (10000) Phosphoric acid (20) Nitric acid (5000) Nitric acid (5000) ο Μ Nitric acid (10000) Nitric acid (5000) S' i & m nitric acid (5000) ΰ a CQ «Λ > m ο ΪΗ «Λ S 3 V3 ο g 沄1 〇V lx. ο a ο *Λ «〇cs ο < Ο o W*1 200 1000 § 1000 2000 500 500 Hospital condensation reaction (including S ppm) Μ £ s a. s 2 2 S 〇Cl. is PI(100) £ S ε Pl(100) sg ! S a. 邑ε S CS Έ Η 100 200 100 300 Ν ο o 200 Ο O 400 ο 〇 200 »Λ g ο 200 ο 100 Cold-rolled stencil cold-rolled steel plate cold-rolled slab cold-rolled steel plate cold-rolled steel plate cold-rolled steel plate cold-rolled steel plate cold-rolled plate cold-rolled steel plate cold-rolled steel plate 1 1 cold-rolled steel plate cold-rolled steel plate 5000-series aluminum cold-rolled steel plate 1 1 Cold rolled stencil 1 Cold rolled steel sheet I Cold rolled steel sheet 6000 series Aluminum cold rolled steel sheet Cold rolled steel sheet Q〇a Ρί η *〇VO η 00 η 〇\ ο Μ 5 ο m 丨9 ε -Ml 201 120245 ο ο ο O «Λ Γ"ί 〇〇〇β ο s 沄§ ν> fS 120 120 120 S w> fn 00 DO C0 nitric acid (5000) bismuth subphosphite 5) nitric acid (10000} S' 0 1 m nitric acid ( 2000) Nitric acid (2000) I 闺 Nitric acid (2000) Nitric acid (5000) Nitric acid (5000 > ο «Λ 200 沄Wl rs 〇1000 500 300 500 P4(100) 1 1 ε S § am 2 胜ο 〇O 200 O Ο 200 200 200 cold-rolled steel plate cold-rolled steel plate cold-rolled steel plate cold-rolled steel plate galvanized steel plate cold-rolled plate cold-rolled steel plate cold-rolled steel plate cold-rolled steel plate CO λ «0 〇二丨卜 ε_3⁄4. .201120245 [Table 6] Metal Film amount (mg/m2) Test coated plate (1) Test coated plate (2) Test coated plate (3) Test coated plate test coated plate (5) Corrosion resistance adhesion Corrosion resistance Corrosion resistance Corrosion resistance Corrosion resistance Corrosion resistance Corrosive erosivity 27 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 31 46 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 35 61 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 38 52 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 39 29 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 43 37 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 67 67 67 45 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 46 42 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 47 34 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 52 13 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 8 56 Δ 〇 Δ 〇 Δ Δ X 〇 Δ Δ 9 64 Δ Δ Δ Δ Δ XX 〇 Δ Δ ratio 10 43 Δ Δ Δ Δ Δ Δ X 〇 Δ Δ 11 21 X Δ XXXXX 〇X Δ Example 12 2300 〇 ◎ 〇 ◎ 〇〇〇 Δ 13 ◎ 13 3200 ◎ ◎ ◎ ◎ ◎ 〇〇 Δ ◎ ◎. 14 11 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ -38- S -·