TW555816B - Nonchromate metallic surface-treating agent, method for surface treatment, and treated steel material - Google Patents

Abstract

The present invention has for its object to provide a nonchromate metallic surface-treating agent which is suited for metallic substrates, and despite the absence of chromium therein, is capable of imparting high processability and corrosion resistance in preparation for a coating or other procedure. This invention provides a nonchromate metallic surface-treating agent which comprises, in each liter thereof, (a) 0.01 to 100 g/l of a silane coupling agent and/or a hydrolytic condensation product thereof, (b) 0.05 to 100 g/l of water-dispersible silica (as solids), and (c) 0.01 to 50 g/l, in terms of Zr ion, of a zirconium compound and/or 0.01 to 50 g/l, in terms of Ti ion, of a titanium compound and/or (d) 0.01 to 100 g/l of a thiocarbonyl-containing compound and/or (e) 0.1 to 100 g/l of a water-soluble acrylic resin.

Description

555816 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明㈠） 發明領域 本發明是關於一種用於鋼鐵基材’如冷軋鋼、熱軋鋼 、不銹鋼、電鍍被覆鋅(zinc-coated)鋼、熱浸被覆辞鋼、被 覆辞銘合金鋼、被覆辞鐵合金鋼、被覆鋅鎂合金鋼、被覆 鋅鋁鎂合金鋼、被覆銘鋼、被覆銘砂合金鋼、被覆錫鋼、 被覆鉛錫合金鋼和被覆鉻鋼之金屬表面處理劑、一種表面 處理的方法、一種生產被覆鋼材的方法’並可進一步在已 處理的表面上塗上頂部塗層(coatings)，及以此種方法生產 之已表面被覆之鋼鐵的產品。 先前技藝 做爲金屬表面處理劑’一種含鉻的表面處理劑如鉻酸 鹽系統和磷酸鹽-鉻酸鹽系統已被廣泛的應用至今。但由於 現代之環境保護的趨勢’使得表面處理更需要嚴密的管理 控制。例如使用含有毒性一特別是被覆系統中含有可致癌 的鉻元素更被禁止。因此’發展出不含鉻的金屬表面處 理劑且具有與鉻處理劑所給予之相同效果的黏著力與耐腐 蝕性是眾所期待的。 如日本專利HEM1-29742中所揭示的，之前之發明家 所發明而發展出的非鉻酸鹽之防止鐵生銹的處理劑包含水 基樹脂，在其中亦結合包含硫羧基化合物、磷酸鹽離子、 和可以水分散的二氧化矽。然而，本系統並不適用於上述 需要嚴謹的製程性和黏著力的應用，即使它具有良好的抗 腐触性。同時，關於砂院聯結劑--種含有兩種不相似石夕 烷聯結劑的酸性的表面處理劑亦於日本柯凱（Kokai)出版 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 0 -------訂---------L· 經濟部智慧財產局員工消費合作社印製 555816 A7 B7 五、發明說明（上） 物HEI-8-73775中揭露。然而，該系統的耐腐蝕性應用於 本發明金屬表面處理後所需要之高耐腐蝕性和良好的製程 性的環境是相當不足的。 並且，日本柯凱出版物HEI-10-60315發表了一種包含 具有與水基乳膠液反應的某些功能基之矽烷聯結劑的鋼鐵 結構表面處理劑，但是所需的耐腐飩性僅適用於較緩和的 腐蝕測試，如抗潮濕性的測試；但當耐腐鈾性爲主要的考 慮特性時，在高度嚴苛的耐腐蝕性要求下，該系統遠無法 提供如本發明所能提供之防鐵銹蝕層。依前面所述之對表 面處理之要求，發展一種在薄的被覆層厚度下，具有足夠 的耐腐蝕性及製程黏著性之金屬表面處理劑是現在所需要 的。 發明摘述 本發明主要目的是提供一種適合金屬基材-特別是被 覆金屬之鋼讀材料的非鉻酸鹽金屬表面處理劑，雖然在其 中沒有鉻元素，仍可以在製備一被覆層或其他製程中提供 高製程性和耐腐蝕性。依本發明之非鉻酸鹽金屬表面處理 劑於每公升中包括： (a) 0.01至100克/升之矽烷聯結劑及/或水解的濃縮產 物； (b) 0.05至100克/升的可以水分散之二氧化矽（固體 )，和 (c) 0.01至50克/升之含锆離子之锆化合物及/或〇·〇ι 至50克/升之含鈦離子之鈦化合物，及/或 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)555816 Printed by A7 B7, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention ㈠) Field of the invention The present invention relates to a steel substrate such as cold rolled steel, hot rolled steel, stainless steel, zinc-coated steel , Hot-dip coated steel, coated alloy steel, coated iron alloy steel, coated zinc-magnesium alloy steel, coated zinc-aluminum-magnesium alloy steel, coated Ming steel, coated sand alloy steel, coated tin steel, coated lead-tin alloy steel And metal surface treatment agent for coated chrome steel, a surface treatment method, a method for producing a coated steel material ', and can further apply top coatings on the treated surface, and the surface coating produced by this method Steel products. Prior art As a metal surface treatment agent ', a chromium-containing surface treatment agent such as a chromate system and a phosphate-chromate system has been widely used so far. However, due to the trend of modern environmental protection, the surface treatment requires strict management and control. For example, the use of toxic elements—especially coating systems that contain carcinogenic chromium—is even more prohibited. Therefore, the development of a chromium-free metal surface treatment agent having the same adhesion and corrosion resistance as those provided by the chromium treatment agent is expected. As disclosed in Japanese patent HEM1-29742, the non-chromate treatment agent for preventing iron rust developed by the previous inventors includes a water-based resin, which also contains a sulfur carboxyl compound and phosphate ions. , And water-dispersible silica. However, this system is not suitable for the above applications that require rigorous processability and adhesion, even if it has good corrosion resistance. At the same time, Shayuan's coupling agent, an acidic surface treatment agent containing two dissimilar lithoxane coupling agents, was also published in Kokai, Japan. 4 This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) 0 ------- Order --------- L · Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 555816 A7 B7 V. Invention Description (above) disclosed in HEI-8-73775. However, the corrosion resistance of this system is quite insufficient for the environment with high corrosion resistance and good processability required after the metal surface treatment of the present invention. Also, the Japanese Kekai publication HEI-10-60315 published a steel structure surface treatment agent containing a silane coupling agent having certain functional groups that reacts with water-based latex, but the required corrosion resistance is only applicable to Relatively mild corrosion tests, such as moisture resistance tests; but when corrosion-resistant uranium is the primary consideration, under highly stringent corrosion resistance requirements, the system is far from providing the protection provided by the present invention Corroded layer of iron. According to the requirements for surface treatment described above, the development of a metal surface treatment agent with sufficient corrosion resistance and process adhesion at a thin coating thickness is now required. SUMMARY OF THE INVENTION The main purpose of the present invention is to provide a non-chromate metal surface treatment agent suitable for metal substrates, especially steel coated materials coated with metal. Although there is no chromium element in it, it can still be used to prepare a coating or other processes. Provides high processability and corrosion resistance. The non-chromate metal surface treating agent according to the present invention includes in each liter: (a) 0.01 to 100 g / L of silane coupling agent and / or hydrolyzed concentrated product; (b) 0.05 to 100 g / L may Water-dispersible silicon dioxide (solid), and (c) 0.01 to 50 g / l of zirconium ion-containing zirconium compound and / or 0.005 to 50 g / l of titanium ion-containing titanium compound, and / or 5 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

555816 A7 B7 五、發明說明（3 ) (d) 0.01至100克/升的含硫羰基化合物；及/或 (e) 0.1至100克/升之水溶性丙烯酸樹脂。 依本發明之非鉻酸鹽表面處理劑可包括〇·01至1〇0克 /升的磷酸鹽離子。 依本發明所述之金屬表面處理的方法是以前述之金屬 表面處理劑，處理鋼鐵材料或被覆金屬之鋼鐵材料的表面 ，此方法最適合用於被覆鋅之鋼材的表面處理。 根據本發明之方法該經表面處理過之鋼材和經表面處 理被覆金屬之鋼材可由上述方法之該金屬袠面處理劑獲得 〇 依本發明之方法生產之經被覆之鋼鐵材料，包括以該 之金屬表面處理劑來處理被覆金屬之鋼鐵材料的表面，接 著，被覆在其頂部上。 本發明之經被覆之鋼鐵材料是以上述方法使用前述之 金屬表面處_劑而得。 發明之細節說明 當矽烷化合物爲非鉻酸鹽金屬表面處理劑之基本，組成 時，本發明之金屬表面處理劑包含了矽烷聯結劑及/或水解 的濃縮產物。矽烷聯結劑之水解的濃縮產物其意思是指， 藉由矽烷聯結劑之水解的聚合作用而獲得之低聚合物。 上述在本發明中所使用之矽烷聯結劑並未特別限定， 但尤應包含下列化合物：乙烯基甲氧矽烷、乙烯基三甲氧 矽烷、乙烯基乙氧矽烷、乙烯基三乙氧矽烷、3-胺基丙基 三乙氧砍院、3-丙嫌酸氧丙基三甲氧砍院、3_甲基丙嫌氧 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線丨一 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 555816 A7 B7 五、發明說明（> ) 丙基三甲氧矽烷、3-硫醇基丙基三甲氧矽烷、N-(l，3-亞二 甲基丁基)-3-(三乙氧甲矽烷基)-1-丙胺、N，N’-雙[3-(三乙氧 甲矽烷基)丙基]1,2-乙二胺、Ν-(β-胺乙基)-γ-胺丙基甲基二 甲氧矽烷、Ν-(β-胺乙基)-γ-胺丙基三甲氧矽烷、γ-胺丙基三 甲氧矽烷、γ-胺丙基三乙氧矽烷、胺丙基甲基二甲氧矽院 、γ-丙烯酸氧丙基三甲氧矽烷、γ-丙烯酸氧丙基三乙氧矽院 、丫-丙烯酸氧丙基甲基二甲氧矽烷、2-(3,4-環氧環己基）乙 基三甲氧矽烷、γ-甲基丙烯氧丙基三甲氧矽烷、丫_甲基丙烯 氧丙基三乙氧矽烷、γ-硫醇基丙基三甲氧矽烷、γ-硫醇基丙 基三乙氧矽烷和Ν-[2-(乙烯基苯甲胺）乙基]-3-胺丙基三 甲氧矽烷。 特別較佳的矽烷聯結劑包括乙烯基甲氧矽烷、乙烯基 乙氧矽烷、3-胺丙基三乙氧矽烷、3-丙烯酸氧丙基三甲氧 矽烷、3-硫醇基丙基三甲氧矽烷、N-(l，3-亞二甲基丁基)-3-(三乙氧甲>夕烷基）-1-丙胺、N，N’-雙[3-(三乙氧甲矽烷 基）丙基]1，2-乙二胺。這些矽烷聯結劑可單獨使用或適當 的加以混合使用。 在本發明中，該矽烷化合物是在每一公升的金屬表面 處理劑中，以〇.〇1至100克/升之濃度配製，較佳之濃度則 爲0.05至25克/升。若矽烷化合物之濃度低於0.01克/升 ，則非鉻酸鹽底漆(primer)對耐腐蝕性及黏著力的提升效果 將大打折扣；但當使用的矽烷化合物濃度超過1〇〇克/升時 ，將會使添加的效果達到飽和而無經濟效益。 本發明之金屬表面處理劑包括可以水分散之二氧化矽 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)555816 A7 B7 V. Description of the invention (3) (d) 0.01 to 100 g / L sulfur-containing carbonyl compound; and / or (e) 0.1 to 100 g / L water-soluble acrylic resin. The non-chromate surface treating agent according to the present invention may include 0.01 to 100 g / liter of phosphate ion. The metal surface treatment method according to the present invention uses the aforementioned metal surface treatment agent to treat the surface of a steel material or a metal-coated steel material. This method is most suitable for the surface treatment of zinc-coated steel. According to the method of the present invention, the surface-treated steel and the surface-treated coated metal can be obtained from the metal surface treatment agent of the method described above. The coated steel material produced according to the method of the present invention includes the metal. A surface treatment agent is used to treat the surface of the steel material coated with metal, and then, it is coated on the top. The coated steel material of the present invention is obtained by the aforementioned method using the aforementioned metal surface treatment agent. Detailed description of the invention When the silane compound is the basic composition of the non-chromate metal surface treatment agent, the metal surface treatment agent of the present invention includes a silane coupling agent and / or a hydrolyzed concentrated product. The hydrolyzed concentrated product of the silane coupling agent means an oligomer obtained by the polymerization of the hydrolysis of the silane coupling agent. The above-mentioned silane coupling agent used in the present invention is not particularly limited, but should particularly include the following compounds: vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3- Aminopropyltriethoxylate, 3-propanoic acid tripropyloxylate, 3_methylpropanexyl 6 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) Order --------- Online 丨 Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 555816 A7 B7 5 Description of the invention (>) propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (l, 3-dimethylenebutyl) -3- (triethoxysilyl)- 1-propylamine, N, N'-bis [3- (triethoxysilyl) propyl] 1,2-ethylenediamine, N- (β-aminoethyl) -γ-aminopropylmethyldi Methoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminepropylmethyldimethoxy Silicon Institute, γ-acrylic acid oxypropyl Methoxysilane, γ-oxypropyltriethoxysilane, γ-oxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methyl Allyloxypropyltrimethoxysilane, y-methacryloxypropyltriethoxysilane, γ-thiolpropyltrimethoxysilane, γ-thiolpropyltriethoxysilane, and N- [2- (Vinyl benzylamine) ethyl] -3-aminopropyltrimethoxysilane. Particularly preferred silane coupling agents include vinyl methoxysilane, vinyl ethoxysilane, 3-aminopropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane , N- (l, 3-dimethylenebutyl) -3- (triethoxymethyl) -1-propylamine, N, N'-bis [3- (triethoxysilyl) ) Propyl] 1,2-ethylenediamine. These silane coupling agents can be used singly or in an appropriate mixture. In the present invention, the silane compound is formulated at a concentration of 0.01 to 100 g / L in each liter of the metal surface treating agent, and a preferred concentration is 0.05 to 25 g / L. If the concentration of the silane compound is less than 0.01 g / l, the effect of the non-chromate primer on the improvement of the corrosion resistance and adhesion will be greatly reduced; but when the concentration of the silane compound used exceeds 100 g / l At the same time, the added effect will be saturated without economic benefits. The metal surface treatment agent of the present invention includes water-dispersible silicon dioxide. 7 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

555816 ____B7__ 五、發明說明（r ) (請先閱讀背面之注意事項再填寫本頁) 。可以水分散之二氧化矽雖未特別限制，但最好是球狀二 氧化矽、鏈狀二氧化矽或經鋁改良之二氧化矽，在其中應 無鈉和其它雜質，且呈弱鹼性。球狀二氧化矽包含如 ”Snowtex N”、”Snowtex UP”（該兩者均由日產化學製造 )之膠狀二氧化砍和锻製的（fumed)二氧化砂，如”Aerosil” (日本Aerosil);鏈狀二氧化矽包含二氧化矽凝膠如 ”Snowtex PS”（日產化學）；和經鋁改良之二氧化砍包含 “Adelite AT-20A”(Asahi Denka)，上述所有之二氧化矽均 爲商業化之產品。 前述之可以水分散之二氧化矽是在固體的基礎上，於 每一公升的金屬表面處理劑中，以0.05至100克/升之濃度 配製，較佳之濃度則爲0.5至60克/升。若可以水分散之二 氧化矽之濃度低於〇.〇5克/升，則對耐腐蝕性效能的提升將 不顯著；但當使用的可以水分散之二氧化矽濃度超過100 克/升時，木僅無法使耐腐蝕性得到任何的提升，還會使金 屬表面處理劑的槽浴穩定性降低。 經濟部智慧財產局員工消費合作社印製 本發明之金屬表面處理劑尙包括锆化合物及/或鈦化合 物。銷化合物包含氧锆基碳酸銨、氫氟化锆、氟化鉻銨、 氟化鉻鉀、氟化锆鈉、乙醯丙酮酸鉻、丁氧化锆-1-丁醇溶 液、η-丙氧化鉻等等。鈦化合物包含氫氟化鈦、氟化鈦銨 、酸草醯酸異丙氧化鈦、異丙基鈦酸鹽、乙氧化鈦、2-乙 基-1-己醇酸鹽、第四異丙基鈦酸鹽、第四-η-丁酯鈦酸鹽、 氟化鈦鉀、氟化鈦鈉等等。這些矽烷聯結劑可單獨使用或 適當的加以混合使用。 8 本紙張尺度適用中國國家標準（CNS)A4規格（21G X 297公髮) '" 一 經濟部智慧財產局員工消費合作社印製 555816 A7 B7 五、發明說明（& ) 上述所提之锆化合物及/或鈦化合物均可調配，在每一 公升的金屬表面處理劑中，就锆離子或鈦離子而言，其濃 度爲0.01至50克/升，最好是0.05至5克/升。如果上述 化合物的濃度少於〇.〇1克/升，耐腐蝕性將不足。若濃度超 過50克/升，不僅無法使加工黏著性得到提升，還會犧牲 槽浴穩定性。 依照本發明之金屬表面處理劑，其包含含硫羰基化合 物及/或水溶性丙烯酸樹脂。含硫羰基化合物可以是至少有 一個硫羰基群，所以包含硫脲、二甲基硫脲、1，3-二甲基 硫脲、二丙基硫、二丁基硫脲、I，3-二苯基冬硫脲、2,2·二 甲苯基硫脲、硫乙醯胺、二甲基二硫氨基甲酸鈉、硫化四 甲基秋蘭姆(tetramethythiuram)、二硫化四丁基秋蘭姆、N-乙基苯基二硫氨基甲酸鋅、二甲基二硫氨基甲酸鋅、五 亞甲基二硫氨基甲酸六氫毗啶鹽、二乙基二硫氨基甲酸鋅 、二乙基二氨基甲酸鈉、異丙基黃原酸鋅、亞乙基硫脲 、二硫化二甲基黃酸(dimethylxanthogen)、二硫基乙二醯二 胺、聚二硫氨基甲酸或他的鹽等等。這些化合物可單獨使 用或加以適當地混合使用。 上述所提之含硫羰基化合物濃度可以爲0.01至100克 /升，最好是以0.1至10克/升來加以調配。如果上述化合 物的濃度低於〇·〇1克/升，耐腐蝕性將不足；若濃度超過 100克/升，則因耐腐蝕性的提升已達飽和而顯得不經濟。 水溶性丙烯酸樹脂是一種共聚合物——種建基於丙烯 酸及/或甲基丙烯酸和包括它們的含甲基丙烯酸酯、甲基甲 9 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ~ ' (請先閱讀背面之注意事項再填寫本頁)555816 ____B7__ 5. Description of the invention (r) (Please read the notes on the back before filling this page). Although water-dispersible silicon dioxide is not particularly limited, it is preferably spherical silicon dioxide, chain-shaped silicon dioxide, or aluminum-modified silicon dioxide, which should be free of sodium and other impurities, and be weakly alkaline. . Spherical silica includes colloidal dioxide chopped and fumed sand such as "Snowtex N" and "Snowtex UP" (both manufactured by Nissan Chemical), such as "Aerosil" (Aerosil, Japan ); Chain silicon dioxide containing silica gel such as "Snowtex PS" (Nissan Chemical); and aluminum modified chopper containing "Adelite AT-20A" (Asahi Denka), all of the above silicon dioxide are For commercial products. The aforementioned water-dispersible silicon dioxide is prepared on a solid basis in a concentration of 0.05 to 100 g / L in each liter of the metal surface treating agent, and a preferred concentration is 0.5 to 60 g / L. If the concentration of water-dispersible silicon dioxide is less than 0.05 g / l, the improvement of the corrosion resistance performance will not be significant; but when the concentration of water-dispersible silicon dioxide used exceeds 100 g / l , Wood can not only improve the corrosion resistance in any way, it will also reduce the bath stability of the metal surface treatment agent. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The metal surface treatment agent 尙 of the present invention includes a zirconium compound and / or a titanium compound. Pin compounds include zirconyl ammonium carbonate, zirconium hydrofluoride, chromium ammonium fluoride, potassium chromium fluoride, sodium zirconium fluoride, chromium acetate pyruvate, zirconium butoxide-1-butanol solution, and η-propion oxide and many more. Titanium compounds include titanium hydrofluoride, titanium ammonium fluoride, titanium isopropyl oxalate, isopropyl titanate, titanium ethoxide, 2-ethyl-1-hexanolate, and fourth isopropyl Titanate, fourth-n-butyl titanate, potassium titanium fluoride, sodium titanium fluoride, and the like. These silane coupling agents can be used singly or in an appropriate mixture. 8 This paper size applies the Chinese National Standard (CNS) A4 specification (21G X 297 issued) '" Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 555816 A7 B7 V. Description of the invention (&) The zirconium mentioned above The compound and / or the titanium compound can be formulated. In each liter of the metal surface treatment agent, the concentration of the zirconium ion or the titanium ion is 0.01 to 50 g / l, preferably 0.05 to 5 g / l. If the concentration of the above compound is less than 0.01 g / L, the corrosion resistance will be insufficient. If the concentration exceeds 50 g / l, not only the processing adhesion cannot be improved, but the bath stability will be sacrificed. The metal surface treating agent according to the present invention comprises a sulfur-containing carbonyl compound and / or a water-soluble acrylic resin. The sulfur-containing carbonyl compound may have at least one thiocarbonyl group, and therefore contains thiourea, dimethylthiourea, 1,3-dimethylthiourea, dipropylthio, dibutylthiourea, and 1,3-dithiourea. Phenyl thiothiourea, 2,2 xylyl thiourea, thioacetamide, sodium dimethyl dithiocarbamate, tetramethythiuram sulfide, tetrabutyl thiuram disulfide, N -Zinc ethylphenyldithiocarbamate, zinc dimethyldithiocarbamate, hexamethylene dithiocarbamate hexahydropyridine salt, zinc diethyldithiocarbamate, sodium diethyldicarbamate, Zinc isopropyl xanthate, ethylene thiourea, dimethylxanthogen disulfide, dithioethylene diamine diamine, polydithiocarbamic acid or other salts thereof, and the like. These compounds may be used singly or in an appropriate mixture. The concentration of the sulfur-containing carbonyl compound mentioned above may be 0.01 to 100 g / liter, preferably 0.1 to 10 g / liter. If the concentration of the above-mentioned compound is lower than 0.01 g / L, the corrosion resistance will be insufficient; if the concentration exceeds 100 g / L, it will not be economical because the improvement of the corrosion resistance has reached saturation. Water-soluble acrylic resin is a copolymer-based on acrylic acid and / or methacrylic acid and including methacrylic acid esters and methyl formaldehyde9. This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) ~ '(Please read the notes on the back before filling this page)

555816555816

經濟部智慧財產局員工消費合作社印製 五、發明說明（"I ) 基丙烯酸酯、乙基甲基丙烯酸酯等等，且包含其衍生物和 其它丙烯單體之共聚合物。建構共聚合物之總單體數最好 不少於70%之丙烯酸及/或甲基丙烯酸。在本發明中，每一 公升的金屬表面處理劑之丙烯酸樹脂調配濃度爲0.1至100 克/升。若丙烯酸樹脂的濃度少於0.1克/升，彎曲黏著性和 深拉伸性無法得到足夠的提升。而從另一個角度來看，若 濃度超過100克/升，則因彎曲黏著性和深拉伸性的提升已 達飽和而顯得不經濟。 在重量平均基礎上，丙烯酸樹脂之分子量最好不要少 於10,000。較適合的範圍在300,000至2,000,000。超過 2,000,000將導致過高的黏稠性而降低加工性。 本發明之金屬表面處理劑可以磷酸鹽離子來加以補充 ，藉此來提升耐腐蝕性。 上述添加之磷酸鹽離子可以以加入水中會產生磷酸鹽 離子之某化j合物來製造。這些化合物如曾提及之磷酸和磷 酸之鹽類，如Na3P〇4、Na2HP04和NaH2P04，及濃縮磷酸 化合物，如濃縮磷酸、聚磷酸、偏磷酸、焦磷酸、超磷酸 等等和其鹽類。這些化合物可單獨使用或加以適當地混合 使用。 每一公升的金屬表面處理劑中，上述之磷酸鹽離子之 調配濃度爲〇·〇1至100克/升，較適合之濃度爲0.1至10 克/升。若濃度少於0.01克/升，耐腐蝕性的提升將不足； 而從另一個角度來看，若濃度超過100克/升則將會產生反 效果，因爲鍍鋅鋼材將會被過度腐蝕而導致表面被覆產生 10 ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of invention (" I) acrylate, ethyl methacrylate, etc., and copolymers containing derivatives and other propylene monomers. The total number of monomers constituting the copolymer is preferably not less than 70% of acrylic acid and / or methacrylic acid. In the present invention, the acrylic resin is formulated at a concentration of 0.1 to 100 g / liter per liter of the metal surface treatment agent. If the concentration of the acrylic resin is less than 0.1 g / liter, the bending adhesion and deep stretchability cannot be sufficiently improved. From another perspective, if the concentration exceeds 100 g / l, it will be uneconomical because the improvement in bending adhesion and deep stretchability has reached saturation. On a weight average basis, the molecular weight of the acrylic resin is preferably not less than 10,000. A more suitable range is 300,000 to 2,000,000. More than 2,000,000 will result in too high viscosity and reduce workability. The metal surface treatment agent of the present invention can be supplemented with phosphate ions, thereby improving the corrosion resistance. The above-mentioned added phosphate ions can be produced by adding a certain chemical compound which generates phosphate ions when added to water. These compounds include phosphoric acid and salts of phosphoric acid, such as Na3P04, Na2HP04, and NaH2P04, and concentrated phosphoric acid compounds, such as concentrated phosphoric acid, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, superphosphoric acid, and the like, and salts thereof. These compounds may be used singly or in an appropriate mixture. In each liter of the metal surface treatment agent, the above-mentioned phosphate ion is prepared at a concentration of 0.01 to 100 g / L, and a more suitable concentration is 0.1 to 10 g / L. If the concentration is less than 0.01 g / l, the improvement of corrosion resistance will be insufficient; from another perspective, if the concentration is more than 100 g / l, it will have adverse effects, because galvanized steel will be excessively corroded and caused The surface coating produces 10 ^ paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 555816 A7 B7 五、發明說明（？） 劣化，或當水基樹脂爲其添加成份時，則將會使其凝結。 本發明之金屬表面處理劑可更進一步的包含其它成份 。就其它組成而言，在此提到的爲單寧酸和其鹽類、植酸 和其鹽類及水基樹脂。可使用之水基樹脂尤其包括胺甲酸 乙酯樹脂、環氧樹脂、乙烯-丙烯酸共聚合物、酚樹脂、 聚酯樹脂、聚烯樹脂、酸醇樹脂和聚碳酸酯樹脂。這些水 基樹脂可單獨使用或加以適當地混合使用。當使用水基樹 脂時，有機溶劑可同時使用來促進它的成膜特性，可提供 一個更均勻、平滑的鍍膜。更進一步的，調和劑、潤濕劑 和防泡沬形成劑亦可使用。 本發明之金屬表面處理劑可使用來當做如冷軋鋼、熱 軋鋼、不銹鋼、電鍍被覆鋅鋼、熱浸被覆鋅鋼、被覆鋅鋁 合金鋼、被覆鋅鐵合金鋼、被覆鋅鎂合金鋼、被覆鋅鋁鎂 合金鋼、被覆鋁鋼、被覆鋁矽合金鋼、被覆錫鋼、被覆鉛 錫合金鋼/被覆鉻鋼和被覆鎳鋼等等之鋼材之表面處理劑 。特別是對於表面有預先被覆金屬之鋼鐵材料更是有效。 使用這個表面處理劑的方法-也就是處理鋼鐵材料表面之 方法’可在基材之金屬表面上組合運用前述之金屬表面處 理劑，然後乾燥鍍層；或預先加熱基材，再使用本發明之 金屬表面處理劑，然後利用基材本身殘留的熱來乾燥鑛層 〇 在這兩種方法中，上述之乾燥製程可在室溫至25(rc 、時間2秒至5分鐘來完成。若超過250°C的限制，黏著 性和耐腐蝕性則會受到不良的影響。較佳之條件是4〇至 11 本紙張尺度適用中關家標準（CNS)A4規格⑵0x297公爱)-------- (請先閱讀背面之注意事項再填寫本頁) 訂---------線— 555816Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 555816 A7 B7 V. Description of the invention (?) Deterioration, or when water-based resin is added to it, it will condense. The metal surface treating agent of the present invention may further include other components. Among other compositions, tannic acid and its salts, phytic acid and its salts, and water-based resins are mentioned. Usable water-based resins include urethane resins, epoxy resins, ethylene-acrylic copolymers, phenol resins, polyester resins, polyolefin resins, acid-alcohol resins, and polycarbonate resins. These water-based resins can be used singly or in an appropriate mixture. When using water-based resins, organic solvents can be used simultaneously to promote its film-forming properties, which can provide a more uniform and smooth coating. Furthermore, blending agents, wetting agents and antifoaming agents can also be used. The metal surface treatment agent of the present invention can be used as cold rolled steel, hot rolled steel, stainless steel, galvanized coated zinc steel, hot-dip coated zinc steel, coated zinc aluminum alloy steel, coated zinc iron alloy steel, coated zinc magnesium alloy steel, coated zinc Surface treatment agent for aluminum-magnesium alloy steel, coated aluminum steel, coated aluminum-silicon alloy steel, coated tin steel, coated lead-tin alloy steel / coated chrome steel, coated nickel steel, etc. It is especially effective for steel materials with pre-coated metal on the surface. The method of using this surface treatment agent-that is, the method of treating the surface of iron and steel materials' can be combined with the aforementioned metal surface treatment agent on the metal surface of the substrate, and then the coating is dried; or the substrate is heated in advance, and then the metal of the present invention is used Surface treatment agent, and then use the residual heat of the substrate itself to dry the ore layer. In these two methods, the above drying process can be completed at room temperature to 25 (rc, time 2 seconds to 5 minutes. If it exceeds 250 ° C limit, adhesiveness and corrosion resistance will be adversely affected. The better condition is 40 to 11 This paper size applies the Zhongguan Standard (CNS) A4 specification (0x297 public love) -------- (Please read the notes on the back before filling this page) Order --------- line — 555816

經濟部智慧財產局員工消費合作社印製 五、發明說明（^ ) 180°C X 5秒至2分鐘。 依據本發明之處理金屬表面的方法，該金屬表面處理 劑在乾燥鍍膜的基礎上之沉積量，不少於〇·1 mg/m2爲較佳 。如果其覆蓋少於0.1 mg/m2，則防銹效果將不足夠。另一 方面，若其覆蓋過多，被覆之預先處理則顯得不經濟。因 此，較佳之覆蓋量爲〇·5至500 mg/m2，特別是1至250 mg/m2 0 依據本發明在實行處理金屬表面的方法中，該金屬表 面處理劑之使用模式並未特別限制。所以，一般常用的技 術如滾輪被覆(r〇ller-coating_、淋浴式被覆（shower-coating) 、噴被覆（spray-coating)、以浸(dipping)和刷(brush)的方式 被覆都可選擇使用。最佳之鋼鐵基材包括被覆金屬鋼材、 特別是各種的裝甲鋼材。 依據本發明之生產經被覆鋼材之方法包括以該金屬表 面處理劑處k金屬表面、烘乾該被覆層和被覆於其頂部。 頂部的被覆可以是，例如，當作在塗上和乾燥非鉻酸鹽底 漆後之被覆層，或者是一個提供防止指紋印上或增加潤滑 性的功能性之被覆層。 上述之生產技術不僅可應用在預先經被覆鍍層之鋼材 ，亦可用於之後經被覆鏟層之鋼材，而且在本說明所述之 “經覆鍍層鋼材”包含兩種型式之鋼材。再者，在此所用 之鋼材”其意謂著任何和全部鋼材，包括鋼片和鋼板。 在非鉻酸鹽底漆的配方中，可使用任何不包含鉻酸鹽 型式的防銹顏料。底漆較好是包含一種釩酸鹽型式之防銹 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (^) 180 ° C X 5 seconds to 2 minutes. According to the method for treating a metal surface according to the present invention, the deposition amount of the metal surface treatment agent on the basis of the dry plating film is preferably not less than 0.1 mg / m2. If it covers less than 0.1 mg / m2, the antirust effect will be insufficient. On the other hand, if it is overly covered, pre-treatment of the cover may not be economical. Therefore, the preferred coverage is from 0.5 to 500 mg / m2, especially from 1 to 250 mg / m2. In the method for treating a metal surface according to the present invention, the use mode of the metal surface treatment agent is not particularly limited. Therefore, commonly used techniques such as roller coating (shower-coating), shower-coating, spray-coating, coating by dipping and brushing can be selected. The best steel substrate includes coated metal steels, especially various armored steels. The method for producing coated steels according to the present invention includes treating the metal surface with the metal surface treatment agent, drying the coating layer, and coating it. Top. The top coating can be, for example, a coating that is applied and dried with a non-chromate primer, or a coating that provides functionality to prevent fingerprints or increase lubricity. Production described above The technology can be applied not only to steels that have been coated in advance, but also to steels that have been coated afterwards, and the "coated steels" described in this description include two types of steels. Furthermore, as used herein "Steel" means any and all steels, including steel sheets and steel plates. In the formulation of non-chromate primers, any anti-rust pigment that does not contain a chromate type can be used. Base The lacquer preferably contains a type of vanadate to prevent rust. 12 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

訂----------線L 經濟部智慧財產局員工消費合作社印製 555816 A7 B7 五、發明說明（，° ) 顏料或磷酸鹽型式之防銹顏料（V/P顏料底漆），或最好 使用一種矽酸鈣型式之防銹顏料。 該底漆的被覆量最好是相當於乾燥後1至20 μιη的厚 度。若乾燥後厚度小於1 μιη，則無提供足夠之耐腐蝕性； 反之，厚度超過20 μιη，加工黏著性則會降低。 該非鉻酸鹽底漆之烘烤條件是：金屬表面的溫度爲 150至250°C，時間爲10秒至5分鐘。 頂部被覆層並特別限定，亦可包含任何傳統之頂部被 覆層。 功能性被覆層特別限定，甚至於包括使用在鉻酸鹽預 處理表面之所有種類被覆層。 該非鉻酸鹽底漆、該頂部鍍層和該功能性被覆層之被 覆技術亦未特別限定，滾輪被覆、淋浴式被覆、空氣-噴 灑被覆、非空氣-噴灑被覆和浸被覆均包含在其中。 依據本A發明之非鉻酸鹽金屬表面處理劑，其包含矽烷 聯結劑及/或水解濃縮產物、可以水分散之二氧化矽、锆之 化合物及/或鈦之化合物，和含硫羰基化合物及/或丙烯酸樹 脂。金屬的表面處理劑適用於金屬表面的處理，特別是裝 甲鋼材，在沒有鉻的參與協助下，亦可提供優秀之製程性 和耐腐蝕性。 再者，在製程中使用本發明之金屬表面處理劑以生產 之非鉻酸鹽被覆鋼材，鋼材可被提供較使用含鉻酸鹽防銹 劑之傳統鋼材相同或甚至於更佳之製程性、深拉伸性和耐 腐蝕性。 13 ^紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) H ϋ ϋ -ϋ 一：OJ· n ϋ ϋ n 1·— I 線—鑣----^——：--------------- 555816 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（u) 上述之優點是因爲本發明之金屬表面處理劑包括矽院 聯結劑，而矽烷聯結劑一部份的反應就是藉由偏矽氧烷的 鍵與基材金屬表面堅固地鍵結在一起，且疏水基有機的部 份與在其上之有機膜緊密結合來增進黏著性，並藉此增進 耐腐蝕性。除此之外，以水分散之二氧化矽粒子被吸附而 且在基材表面呈方向性排列，形成一道能障來防止腐蝕性 離子和水氣，藉此來抑止腐蝕行爲，當矽烷（silanol)基 存在於二氧化矽表面時，會強化在其之有機膜與金屬表面 之黏著性。對於锆離子而言，在金屬表面形成之氧化锆膜 將會提升耐腐蝕性，同時鉻亦可作爲沉積在其上之膜層之 交叉聯結劑，來增加有機膜之交叉聯結密度，並藉此來更 進一步促進耐腐蝕性、黏著性和耐刮性。尙需列入考慮的 是含硫羰基化合物和磷酸鹽離子吸附在金屬表面所造成之 金屬表面的鈍化，更甚者，它們同時存在將會產生增效作 用，使得耐蝕性大幅的提升。 可能的是當丙烯酸樹脂做爲一個與無機成份-如分散 之二氧化矽、锆及類似的物質之鍵結劑時，其作用可增進 製程中之黏著性和深拉伸性。 依據本發明所獲得之經被覆的鋼材有著優良之製程性 和耐腐蝕性，就其本身而論，可應用在相當廣泛的領域， 如家用電子設備、電腦相關裝置、建築元件和汽車及其它 工業產品。 實施例 接下來之例子是用來更進一步詳細加強說明本發明， 14 D氏張尺度適用中國國家標準（CNS)A4規格（210x297公爱） -- (請先閱讀背面之注意事項再填寫本頁) •t----Order ---------- Line L Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 555816 A7 B7 V. Description of the invention (, °) Pigment or phosphate type antirust pigment (V / P pigment primer ), Or preferably a calcium silicate type antirust pigment. The coating amount of the primer is preferably a thickness corresponding to 1 to 20 µm after drying. If the thickness after drying is less than 1 μιη, sufficient corrosion resistance is not provided; on the contrary, if the thickness exceeds 20 μιη, the processing adhesion will be reduced. The baking conditions of the non-chromate primer are: the temperature of the metal surface is 150 to 250 ° C, and the time is 10 seconds to 5 minutes. The top coating is particularly limited and may include any conventional top coating. Functional coatings are particularly limited and even include all types of coatings used on chromate pre-treated surfaces. The coating technology of the non-chromate primer, the top plating layer, and the functional coating layer is also not particularly limited, and roller coating, shower coating, air-spray coating, non-air-spray coating, and dip coating are all included therein. The non-chromate metal surface treatment agent according to the present invention A, comprising a silane coupling agent and / or a hydrolyzed concentrated product, water-dispersible silicon dioxide, zirconium compounds, and / or titanium compounds, and sulfur-containing carbonyl compounds and / Or acrylic resin. Metal surface treatment agents are suitable for the treatment of metal surfaces, especially armored steels. Without the assistance of chromium, they can also provide excellent processability and corrosion resistance. Furthermore, the non-chromate-coated steel produced by using the metal surface treatment agent of the present invention in the manufacturing process can be provided with the same or even better processability and deeper steel than the traditional steel using chromate-containing rust inhibitors. Stretchability and corrosion resistance. 13 ^ Paper size applies Chinese National Standard (CNS) A4 (21〇X 297 mm) (Please read the notes on the back before filling this page) H ϋ ϋ -ϋ One: OJ · n ϋ ϋ n 1 · — Line I— 镳 ---- ^ ——: 555816 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (u) The advantages mentioned above This is because the metal surface treatment agent of the present invention includes a silicon coupling agent, and a part of the reaction of the silane coupling agent is firmly bonded to the metal surface of the base material through the bond of metasiloxane and the hydrophobic group is organic. The part is tightly combined with the organic film thereon to improve adhesion and thereby improve corrosion resistance. In addition, water-dispersed silica particles are adsorbed and arranged in a directional manner on the surface of the substrate, forming an energy barrier to prevent corrosive ions and water vapor, thereby suppressing corrosion behavior. When silanol When the group is on the surface of silicon dioxide, it will strengthen the adhesion between the organic film and the metal surface. For zirconium ions, the zirconia film formed on the metal surface will improve the corrosion resistance. At the same time, chromium can also be used as a cross-linking agent for the film layer deposited on it to increase the cross-linking density of the organic film. To further promote corrosion resistance, adhesion and scratch resistance.尙 What needs to be considered is the passivation of the metal surface caused by the adsorption of sulfur-containing carbonyl compounds and phosphate ions on the metal surface. What's more, their simultaneous existence will have a synergistic effect and greatly improve the corrosion resistance. It is possible that when acrylic resin is used as a bonding agent with inorganic components such as dispersed silica, zirconium, and the like, its effect can improve the adhesion and deep stretchability in the process. The coated steel obtained according to the present invention has excellent processability and corrosion resistance. As such, it can be used in a wide range of fields, such as home electronics, computer-related devices, building elements, automobiles and other industries. product. EXAMPLE The following example is used to further illustrate the present invention in more detail. The 14 D-scale is applicable to the Chinese National Standard (CNS) A4 specification (210x297 public love)-(Please read the precautions on the back before filling this page. ) T ----

0 ^1 ·1 ^1 ϋ ϋ ϋ ϋ ^1 I I ^1 ϋ ϋ i_l ϋ ^1 H ^1 ^1 ϋ ϋ I n ϋ ϋ I ϋ I 555816 A7 B7 五、發明說明（θ) 而並非解釋爲本發明所定義之範疇。 實施例1 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 將1公升的純水加入2.5克的“Sila-Ace S-330”（γ-胺 基丙基三乙氧矽烷；吉索(Chisso)公司），將這混合物置於 室溫下予以攪拌5分鐘。然後，再加入1克的”Snowtex N” (可以水分散之二氧化矽，日產化學）並予以攪拌5分鐘 。另外，在銷離子方面，加入2.5克“Zircosol AC-7”（锆 醯銨碳酸鹽；大齊(Daiichi)稀土元素公司）。然後，再將 5.0克的硫脲（thiouda)和1.25克提供磷酸鹽離子的銨磷 酸鹽加入上述之混合物並攪拌5分鐘，以獲得非鉻酸鹽金 屬表面處理劑。這金屬表面處理劑以鹼性淸潔劑（表面淸 潔劑155 ;日本被覆）來去除油污，且使用#3棒狀被覆 工具，應用在乾的市售熱浸鍍鋅之鍍鋅鋼板（日本測試鑲 板公司；70 X 150x0.4 mm)，使其表面產生一個相當於厚 度20毫克/平方公尺之乾燥膜層。以60°C溫度烘乾金屬表 面之後，使用# 16棒狀被覆工具將V/P含顏料非鉻酸鹽底 漆塗上，乾燥後之膜厚度爲5 μηι，並在溫度215°C下烘乾 金屬表面。接下來，使用# 36棒狀被覆工具，將Fiexicoat 1060 ( —種頂部被覆聚合物；日本被覆）塗上，乾燥後的 膜厚爲15 μιη來當作頂部鍍層，且以230°C的溫度烘乾金 屬表面，預備做爲測試試片。測試試片之彎曲黏著性、耐 腐鈾性和耐刮性的評估方法後續將提及，而其結果顯示如 表1。 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱7 555816 Α7 Β7 五、發明說明（Μ ) 實施例2至22和ί±鉸例1與2 除了矽烷聯結劑，不同的種類和濃度之可以水分散之 二氧化矽、鉻化合物、含硫羰基化合物和水溶性丙烯酸樹 脂及不同濃度之磷酸鹽離子亦表示於表1，使用相同於實 施例1之製程來調配金屬表面處理劑。測試試片使用這些 金屬表面處理劑，並以如實施例1之方法來製備。這些試 片和金屬表面處理劑的評估方法如上所述。結果如表1。 比較例3 除了使用市售之被覆用鉻酸鹽劑（含樹脂型式）替代 本發明之金屬表面處理劑外，鉻的被覆速率爲20毫克/平 方公尺，烘乾後塗上含鉻酸鹽底漆（一種包含鉻酸緦的顏 料），使用相同於實施例1之製程來製備測試試片。結果 如表1所示。 (請先閱讀背面之注意事項再填寫本頁) -1 ---- 訂——^------線」 經濟部智慧財產局員工消費合作社印製 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 555816 A7B7 發 經濟部智慧財產局員工消費合作社印製0 ^ 1 · 1 ^ 1 ϋ ϋ ϋ ϋ ^ 1 II ^ 1 ϋ ϋ i_l ϋ ^ 1 H ^ 1 ^ 1 ϋ ϋ I n ϋ ϋ I ϋ I 555816 A7 B7 5. Explanation of the invention (θ) instead of being interpreted as The scope defined by the present invention. Example 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Add 1 liter of pure water to 2.5 grams of "Sila-Ace S-330" (γ-aminopropyl Triethoxysilane; Chisso), and the mixture was stirred at room temperature for 5 minutes. Then, add 1g of "Snowtex N" (water-dispersible silica, Nissan Chemical) and stir for 5 minutes. In addition, in terms of pin ions, 2.5 g of "Zircosol AC-7" (zirconium ammonium carbonate; Daiichi Rare Earth Element Company) was added. Then, 5.0 g of thiouda and 1.25 g of ammonium phosphate providing phosphate ions were added to the above mixture and stirred for 5 minutes to obtain a non-chromate metal surface treatment agent. This metal surface treatment agent uses an alkaline cleaner (Surface cleaner 155; Japan coating) to remove oil stains, and uses # 3 rod-shaped coating tools to apply to dry, commercially available hot-dip galvanized galvanized steel sheets (Japan Test Panel Company; 70 X 150x0.4 mm) to produce a dry film layer on the surface equivalent to 20 mg / m². After drying the metal surface at 60 ° C, use a # 16 rod coating tool to coat the V / P pigmented non-chromate primer. The thickness of the film after drying is 5 μm, and then bake at 215 ° C. Dry metal surface. Next, using # 36 rod-shaped coating tools, apply Fiexicoat 1060 (— a kind of top coating polymer; Japanese coating), the film thickness after drying is 15 μm as the top coating, and bake at 230 ° C. Dry metal surface, ready for test strips. The evaluation methods for the flexural adhesion, uranium resistance, and scratch resistance of the test pieces will be mentioned later, and the results are shown in Table 1. 15 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 Public Love 7 555816 A7 B7) V. Description of the Invention (M) Examples 2 to 22 and ± ± Examples 1 and 2 Except for the silane coupling agent, different The types and concentrations of water-dispersible silicon dioxide, chromium compounds, sulfur-containing carbonyl compounds, water-soluble acrylic resins, and phosphate ions of different concentrations are also shown in Table 1. The same process as in Example 1 was used to prepare the metal surface treatment. These test pieces used these metal surface treatment agents and were prepared in the same manner as in Example 1. The evaluation methods of these test pieces and metal surface treatment agents were as described above. The results are shown in Table 1. Comparative Example 3 The coating is replaced with a chromate agent (containing resin type) instead of the metal surface treatment agent of the present invention. The coating rate of chromium is 20 mg / m², and a chromate-containing primer (a type containing chromic acid) is applied after drying.缌 pigment), using the same process as in Example 1 to prepare test specimens. The results are shown in Table 1. (Please read the precautions on the back before filling this page) -1 ---- Order ---- ^- ----- line "warp Printed by the Employees' Cooperatives of the Ministry of Economic Affairs and Intellectual Property of the Ministry of Economic Affairs 16 Printed on the paper standard of China National Standard (CNS) A4 (210 X 297 mm) 555816 A7B7

m 寸 un to »r> <N F—4 寸 起 Μ U m m m 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 »n m (N m 链 瘃 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 (N 寸 II (N (N (N <N CN (N CN <N CN (N CN <N (N (N <N CN «η ^Τί 寸 un m CN (N cn S » un in m 州 <Ti »n »n »n un «〇 »n »n »n »n m »n »n «η «η m <r> »n »〇 »〇 (N 蘅 αί 1 <N »〇 d s d o ^T) in o o <N »n <N «Ti d •n f—H <〇 〇· 〇· »n 〇· »n d o »〇 o »〇 O S S 〇 〇· w 蹦 趑 到 m m m SS Μ ΤϊτΤ 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 1 <〇 (N <N <N 1 1 趦 Κ m ^vIS i1m1l 卿 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 f〇H * < < 〇< < < 〇< <N i & ί cu < < On < < Oh < < CU 1 cu < < cu 1 1 1 m ϋ «ο (N s S O o S O »n t〇 (N »n »n »n d Ό (N ri 1 • «〇 <N >n <N »n (N o d 騷 卿 ^4 (N m 寸 Ό 卜 00 〇\ O rj m v〇 f-H CN t 1 (N (N (N in v〇 _ m m 嗽 嚷 1 1 Φ: 硗 <N d O Oj 〇 o wn o (N 〇 O 〇 »n d »n in Vi (N o CN o »n (N o d »r> o >n o o f—^ s o 〇· m Um 卿 (N (N m (N ψ"^ (N 寸 *ί »·*^ (N (N 祕 11 vk f«4 o m O CN tn d Ψ^4 O CN <N »〇 d <N ^T) (N CN f-M 1—^ 〇 s o 驟 术1S ilgrll P (N (N <N v4 ^-H 蘅 vk 孩 (N F—H s d (N »n <N (N f—^ 〇 〇· s o <N ^4 »〇 (N »—4 «η to o s o d 罃 m 不-IS \1mi1 w (N m (N <N f—^ CN (N (N ^—4 <N <N »—4 CN CN CN <N (N ㈣ <N cn 寸 ir\ 00 Os 〇 — (N m 寸 v〇 卜 00 〇s (N <N m fN <N (N 1* f— 01X001 * 饀跋 Msfr^: 3* (請先閱讀背面之注意事項再填寫本頁) I ^--------訂---------線」 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 555816 A7 B7 ___ 五、發明說明（) 眚施例23至26 將如上述之相同方法處理過之薄片，以一種可防指紋 之功能性被覆層代替底漆被覆和頂部被覆，使用#3棒狀 被覆工具塗上，乾燥後的膜厚爲1 μπι，且以溫度120°C烘 乾金屬表面來製作測試試片。這些測試試片評估的結果表 示於在之前之表2。 實施例27至30 將如上述之相同方法處理過之薄片，以一種可增加潤 滑性之功能性被覆層代替底漆被覆和頂部被覆，使用# 3 棒狀被覆工具塗上，乾燥後的膜厚爲1 μπι，且以溫度120 °(：烘乾金屬表面來製作測試試片。這些測試試片評估的結 果表示於在之前之表2。 比較例4 用市售之被覆型鉻酸鹽劑（含樹脂等級）代替金屬表 面處理劑，k鉻的被覆速率爲20毫克/平方公分塗上，並 且以相同於實施例27之處理方法，於乾燥後製備測試試片 ，而評估方式亦相類似。這些測試試片評估的結果表示於 在之前之表2。 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 555816m inch un to »r > < NF-4 inch from Μ U mm mm inch inch inch inch inch inch inch inch inch inch inch (N m chain inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch (N inch II (N ( N (N < N CN (N CN < N CN (N CN < N CN «η ^ Τί inch un m CN (N cn S» un in m state < Ti »n »N» n un «〇» n »n» n »nm» n »n« η «η m < r >» n »〇» 〇 (N 蘅 αί 1 < N »〇dsdo ^ T) in oo < N »n < N« Ti d • nf-H < 〇〇 · 〇 · »n 〇 ·» ndo »〇o» 〇OSS 〇〇 · w Jump to mmm SS Μ ΤϊτΤ 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 1 < 〇 (N < N < N 1 1 趦 Κ m ^ vIS i1m1l 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 f〇H * < < 〇 < < < 〇 < < N i & ί cu < < On < < Oh < < CU 1 cu < < cu 1 1 1 m ϋ «Ο (N s SO o SO» nt〇 (N »n» n »n d Ό (N ri 1 • «〇 < N > n < N» n (N od Sao Qing ^ 4 (N m inch Ό 00 〇 \ O rj mv〇fH CN t 1 (N (N (N (N ( in v〇_ mm 嚷 1 1 Φ: 硗 < N d O Oj 〇o wn o (N 〇O 〇 »nd» n in Vi (N o CN o »n (N od» r > o > noof -^ So 〇 · m Um Qing (N (N m (N ψ " ^ (N 寸 * ί »· * ^ (N (N 1111 vk f« 4 om O CN tn d Ψ ^ 4 O CN < N »〇d < N ^ T) (N CN fM 1— ^ 〇so 术 术 1S ilgrll P (N (N < N v4 ^ -H 蘅 vk child (NF-H sd (N» n < N ( N f— ^ 〇〇 · so < N ^ 4 »〇 (N» —4 «η to osod 罃 m not-IS \ 1mi1 w (N m (N < N f— ^ CN (N (N ^ — 4 < N < N »—4 CN CN CN < N (N ㈣ < N cn inch ir \ 00 Os 〇— (N m inch v〇 卜 00 〇s (N < N m fN < N (N 1 * f— 01X001 * 饀 巴 Msfr ^: 3 * (Please read the precautions on the back before filling in this page) I ^ -------- Order --------- Line " This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 555816 A7 B7 ___ V. Description of the invention () 眚 Examples 23 to 26 The sheet treated in the same way as above is replaced with a primer coating and a top coating with a functional coating that prevents fingerprints. Use # 3 rod shape The coated tool was coated, the film thickness after drying was 1 μm, and the metal surface was dried at a temperature of 120 ° C to make a test specimen. The results of these test strip evaluations are shown in Table 2 above. Examples 27 to 30 A thin film treated in the same manner as described above was replaced with a functional coating layer for increasing lubricity, instead of the primer coating and the top coating, and coated with a # 3 rod-shaped coating tool, and the film thickness after drying It is 1 μm, and a test piece is made at a temperature of 120 ° (: a metal surface is dried. The evaluation results of these test pieces are shown in Table 2 above. Comparative Example 4 A commercially available coating type chromate agent ( Resin grade) instead of the metal surface treatment agent, the coating rate of k chromium was 20 mg / cm², and a test specimen was prepared after drying in the same manner as in Example 27, and the evaluation method was similar. The evaluation results of these test strips are shown in the previous Table 2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 18 This paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 555816

7 7 A B 經濟部智慧財產局員工消費合作社印製7 7 A B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(請先閱讀背面之注意事項再填寫本頁) 61 裝--------訂---------線» 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 555816 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（rj ) 有關於在上述之表1、2所提及之矽烷聯結劑、可以水 分散之二氧化矽、锆化合物、鈦化合物、含硫羰基化合物 和丙烯酸樹脂，是使用下列之市售產品。 [矽烷聯結劑] 1: Sila-Ace S_330 (γ-胺基丙基三乙氧矽烷；吉索(Chisso)公 司） 2: Sila-Ace S0-330 (γ-丙烯酸氧丙基三甲氧矽烷；吉索 (Chisso)公司） 3: Sila-Ace S-810 (γ-硫醇基丙基三甲氧矽烷、；吉索 (Chisso)公司） 4: Sila-Ace S0-330 (γ- Ν-(1，3·亞二甲基丁基)-3-(三乙氧甲 矽烷基)-1-丙胺；吉索(Chisso)公司） [可以水分散之二氧化矽] l:Snowtex N (日產化學公司） 2:Snowtex 0 (日產化學公司） [銷化合物] l:Zircosol AC-7 (锆醯銨碳酸鹽；大齊(Daiichi)稀土元素公 司） 2:氟化鉻銨（試劑） 3:氫氟化锆（試劑） 4:氫氟化鈦（試劑） 5:氟化鈦銨（試劑） [含硫羰基化合物] 1:硫脲（試劑） 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -ϋ ϋ ϋ I -ϋ n n n «1 I · I 1 (請先閱讀背面之注意事項再填寫本頁) 訂______——線-i____________________ 555816 五、發明說明（彳） 2:亞乙基硫脲（試劑） 3:二乙基胺甲酯鈉（試劑） 七I，3-二苯基硫脲（試劑） 5··二甲基二硫氨基甲酸鋅（試劑） 6:異丙基黃原酸鋅（試劑） 7:硫化二甲基黃酸(dimethylxanthogen)(試劑） 8:硫化四甲基秋蘭姆（試劑） 9··二甲基二硫氨基甲酸鈉（試劑） 10:二丁基二硫氨基甲酸鈉（試劑） 11:二硫化四丁基秋蘭姆（試劑） 12:四硫化二五亞甲基秋蘭姆（試劑） 13:N-乙基-N-苯基二硫氨基甲酸鋅（試劑） 14:五亞甲基二硫氨基甲酸六氫吡啶（試劑） 15:二甲基二硫氨基甲酸鋅（試劑） 16··二丁基“脲（試劑） [水溶性丙烯酸樹脂] 1:聚丙嫌酸（試劑），Mw=l，000,000 2:聚甲丙烯酸（試劑），Mw=l，000,000 <評估方法> 下列的評估方法和標準適用於在上述之實施例1至22 和比較例1至3中彎曲黏著性、深拉伸性、耐腐蝕性（1) 和耐刮性的評估，並適用於在上述之實施例23至33和比 較例4之被覆黏著性及耐腐蝕性（2)的評估。 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ---------訂---------線 —. 經濟部智慧財產局員工消費合作社印製 555816 A7 __ B7 五、發明說明（〇 ) 蠻曲黏著性 (主要黏著性） 測試試片彎曲至18〇°(OTT)，中間不得有空隙，環境溫度 控制在20°C。彎曲後的試片以膠帶重覆黏貼、撕開三次， 剝離的程度以20倍的放大鏡檢視，並以下列的標準評分。 分數 5點：沒有裂縫 4點：裂縫遍佈在彎曲帶上 3點：彎曲面之剝離面積小於20% 2點：彎曲面之剝離面積介於20%至80%之間 1點：彎曲面之剝離面積大於80% (次要黏著性） 將測試試片置入沸水中2個小時，然後靜置室內24小 時。接著將測試試片以如上述之方法彎曲和處理，並以相 同於主要黏_性之評分標準評分。 深拉伸性 在環境溫度爲20°C、拉伸比例爲2.3、起皺的限制壓 力：2噸、沖擊R角：5公厘、模具肩部R角：5公厘且沒 有潤滑的條件下，實施圓錐形杯子的測試。然後將測試片 的側表面橫向切開，置入沸水中1小時。從橫切面處量測 膜層的剝離距離。使用下列的評分標準。 分數 5點：起泡寬度<1公厘 4點：起泡寬度Μ公厘，< 2公厘 22 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作社印製(Please read the precautions on the back before filling out this page) 61 Packing -------- Order --------- line »This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 555816 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (rj) Related to the silane coupling agent mentioned in Tables 1 and 2 above, water-dispersible silica, zirconium The compounds, titanium compounds, sulfur-containing carbonyl compounds, and acrylic resins are the following commercially available products. [Silane coupling agent] 1: Sila-Ace S_330 (γ-aminopropyltriethoxysilane; Chisso) 2: Sila-Ace S0-330 (γ-acrylic acid propyltrimethoxysilane; Kyril Chisso) 3: Sila-Ace S-810 (γ-thiol propyltrimethoxysilane; Chisso) 4: Sila-Ace S0-330 (γ-N- (1, 3. Dimethylbutyl) -3- (triethoxysilyl) -1-propylamine; Chisso) [Water-dispersible silicon dioxide] l: Snowtex N (Nissan Chemical Co., Ltd.) 2: Snowtex 0 (Nissan Chemical Co., Ltd.) [Marketing Compound] l: Zircosol AC-7 (Zirconium Ammonium Carbonate; Daiichi Rare Earth Element Company) 2: Chromium Ammonium Fluoride (Reagent) 3: Zirconium Hydrofluoride (Reagent) 4: Titanium hydrofluoride (reagent) 5: Titanium ammonium fluoride (reagent) [Sulfur-containing carbonyl compound] 1: Thiourea (reagent) 20 The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -ϋ ϋ ϋ I -ϋ nnn «1 I · I 1 (Please read the notes on the back before filling out this page) Order ______—— 线 -i ____________________ 555816 V. Description of invention (彳) 2: Asia Ethylthiourea (reagent) 3: Ethylamine methyl sodium (reagent) Hepta I, 3-diphenylthiourea (reagent) 5 ·· Zinc dimethyldithiocarbamate (Reagent) 6: Zinc isopropylxanthate (Reagent) 7: Dimethylxanthogen sulfide (reagent) 8: Tetramethylthiuram sulfide (reagent) 9 ·· Sodium dimethyldithiocarbamate (reagent) 10: Sodium dibutyldithiocarbamate (reagent) 11 : Tetrabutylthiuram disulfide (reagent) 12: Dipentamethylene thiuram tetrasulfide (reagent) 13: N-ethyl-N-phenyl zinc dithiocarbamate (reagent) 14: Wuya Methyldithiocarbamate hexahydropyridine (reagent) 15: Zinc dimethyldithiocarbamate (reagent) 16 ·· Dibutyl "urea (reagent) [Water-soluble acrylic resin] 1: Polyacrylic acid (reagent) , Mw = 1,000,000 2: Polymethacrylic acid (reagent), Mw = 1,000,000 < Evaluation method > The following evaluation methods and standards are applicable to bending in Examples 1 to 22 and Comparative Examples 1 to 3 described above Evaluation of tackiness, deep drawing, corrosion resistance (1) and scratch resistance, and is applicable to the coating tackiness and adhesion of the coatings of Examples 23 to 33 and Comparative Example 4 described above. Evaluation of Corrosion Resistance (2) 21 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- -Order --------- line—. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 555816 A7 __ B7 V. Description of the invention (〇) Roughness of adhesion (mainly adhesion) The test specimen is bent to 18 〇 ° (OTT), there must be no gap in the middle, and the ambient temperature is controlled at 20 ° C. The bent test piece was repeatedly pasted with adhesive tape and torn three times. The degree of peeling was examined with a 20-fold magnifying glass and scored according to the following criteria. 5 points: no cracks 4 points: cracks spread on the curved band 3 points: the peeling area of the curved surface is less than 20% 2 points: the peeling area of the curved surface is between 20% and 80% 1 point: the peeling of the curved surface The area is greater than 80% (secondary adhesion). Put the test piece in boiling water for 2 hours, and then leave it in the room for 24 hours. The test strips were then bent and processed as described above, and scored using the same scoring criteria as the main viscosity. Deep drawability under ambient temperature of 20 ° C, stretch ratio of 2.3, wrinkle limiting pressure: 2 tons, impact R angle: 5 mm, mold shoulder R angle: 5 mm and no lubrication , Implement the test of conical cups. Then, the side surface of the test piece was cut transversely and placed in boiling water for 1 hour. The peeling distance of the film was measured from the cross section. Use the following scoring criteria. Score 5 points: Foaming width < 1 mm 4 points: Foaming width M mm < 2 mm 22 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (please first (Please read the notes on the back and fill in this page.) Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

ϋ ϋ ϋ ϋ H ϋ I ϋ ϋ ^1 1 n n H ϋ ϋ H ϋ ϋ I ϋ ϋ H ϋ ^1 ^1 ϋ ϋ «ϋ I 555816 A7 ——_______Β7____ 五、發明說明（/ ) 3點：起泡寬度22公厘，<3公厘 2點：起泡寬度23公厘，< 5公厘 1點：起泡寬度25公厘 耐腐蝕性（1) (切割區） 將試片橫向切割後，比照JIS Z 2317規範實施鹽霧試 驗500小時。量測在切割線某一邊之起泡寬度，並使用下 列的評分標準。 分數 5點 :起泡寬度=0公厘 4點 :起泡寬度<1公厘 3點 :起泡寬度Μ公厘，<3公厘 2點 :起泡寬度23公厘，<5公厘 1點 :起泡寬度d公厘 (邊 ) 依照JIS Z 2317規範測試試片實施鹽霧試驗500小時。量 測在上面毛邊的起泡寬度，並使用與切割區相同的評分標 準。 耐刮件 使用刮痕測試機，施加1公斤的荷重在測試試片上面 刮。刮傷部份以下列評分標準予以評估。 分數 5點：曝露的底漆之面積< 10% ;基底金屬未顯露 4點：曝露的底漆之面積210%，但<7〇% ;基底金屬未顯 23 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂---------線」 經濟部智慧財產局員工消費合作社印製 555816ϋ ϋ ϋ ϋ H ϋ I ϋ ϋ ^ 1 1 nn H ϋ ϋ H ϋ ϋ I ϋ ϋ H ϋ ^ 1 ^ 1 ϋ ϋ «ϋ I 555816 A7 ——_______ Β7 ____ V. Description of the invention (/) Width 22 mm, < 3 mm 2 points: Foam width 23 mm, < 5 mm 1 point: Foam width 25 mm Corrosion resistance (1) (cutting area) After cutting the test piece transversely The salt spray test was performed for 500 hours in accordance with JIS Z 2317. Measure the blister width on one side of the cut line and use the following scoring criteria. Score 5 points: Foaming width = 0 mm 4 points: Foaming width < 1 mm 3 points: Foaming width M mm < 3 mm 2 points: Foaming width 23 mm < 5 1 point in mm: Bubble width d mm (edge) The test piece was tested in accordance with JIS Z 2317 and subjected to a salt spray test for 500 hours. Measure the blistering width of the burrs above and use the same scoring criteria as the cut area. Scratch Resistant Use a scratch tester to apply a load of 1 kg on the test piece. The scratched part was evaluated using the following scoring criteria. 5 points: the area of the exposed primer <10%; the base metal is not exposed 4 points: the area of the exposed primer is 210%, but <70%; the base metal is not displayed 23 This paper applies Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order --------- line "Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperative 555816

五、發明說明（w) 露 3點：曝露的底漆之面積270% ;曝露的基底金屬之面積< 30% 2點：曝露的底漆之面積<70% ;曝露的基底金屬之面積 >30% ^ <70% 1點：曝露的底漆之面積270% ;曝露的基底金屬之面積 >70% 被覆黏荖件 (主要黏著性） 在實施例23至30中所預被覆之鋼片使用棒狀被覆工 具將三聚氰胺酸醇樹脂（肯撒（Kansai)被覆；Amilac #1〇〇〇)以乾燥後膜厚度爲30 μπι塗上，以加熱爐加熱至 130°C烘乾20分鐘。鋼片允許靜置一整晚，然後加工至一 個 Erichsen 値=7 公厘。膠帶（Nichiban ; CellotapeTM)貼 在加工區域i，並以傾斜45。的方向快速將膠帶撕下。被 覆黏著性依照剝離面積的比例％以下列評分標準予以評估 〇 5點：沒有剝離 4點：剝離面積比例<5% 3點：剝離面積比例25%，<30% 2點：剝離面積比例230%，<50% 1點：剝離面積比例250% (次要黏著性） 同主要黏著性測試，鋼片表面被覆上三聚氰胺酸醇樹 24 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線！ 經濟部智慧財產局員工消費合作社印製 555816 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（，） 脂後，允許靜置一整晚。然後，將每一鋼片置入沸水中30 分鐘，並加工至一個Erichsen値=7公厘。膠帶（Nichiban ;Cellotape™)貼在加工區域上，並以傾斜45°的方向快速 將膠帶撕下。被覆黏著性依照剝離面積的比例％以下列評 分標準予以評估。 5點：沒有剝離 4點：剝離面積比例<5% 3點：剝離面積比例，<30% 2點：剝離面積比例230%，<50% 1點：剝離面積比例>50% 耐腐蝕件（2) (平坦區域） 依照JIS Z 2317規範在室溫溫度35°C下，以濃度5% 之氯化鈉水溶液噴在於實施例23至30所獲得之預被覆鋼 片表面實施鹽霧試驗，在實施鹽霧試驗240小時後，耐腐 蝕性依白斑形成的比例以下列評分標準予以評估。 5點： 沒有白斑 4點： 白斑< 10% 3點： 白斑210%，<20% 2點： 白斑220%，<30% 1點： 白斑230% (加工部份） 於實施例23至30所獲得之預被覆鋼片加工至一個 Erichsen値=7公厘，然後依照JIS Z 2317規範在室溫溫度 25 (請先閱讀背面之注意事項再填寫本頁) -n n .^1 ϋ ϋ-^-r°J· ϋ ϋ ϋ n ϋ I I n ϋ n I ϋ I ϋ n ϋ n n ϋ I n < 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 555816 A7 -- —-^ 五、發明說明（θ ) 35°C下，以濃度5%之氯化鈉水溶液實施鹽霧試驗。在實 驗72小時後，耐腐蝕性依白斑形成的比例以下列評分標準 予以評估。 5點：沒有白斑 4點：白斑<10% 3 點··白斑210%，<20% 2 點··白斑220%，<30% 1點：白斑230% 虹指紋件 於實施例23至26所獲得之預鍍鋼片以指紋壓印在被 覆表面上，依指紋明顯的程度以下列評分標準予以評估。 5點 :無可識別的指紋 4點 :輕微可辨的指紋 3點 :淸晰可辨的指紋 2點 :明顯ft指紋 1點 z非常顯著的指紋 潤滑件 使用裝配有圓錐形衝頭之液壓成形測試機，於實施例 27至30所獲得之預鍍鋼片，在室溫下以下列的條件實施 成形測試。潤滑性的評估以擦傷的程度做爲指標。 衝頭直徑：Φ70公厘 空白邊的直徑：Φ150公厘 偏壓荷重：5公斤重/平方公分 成形速度·· 3.3XHT2公尺/秒 26 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） — (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (w) 3 points exposed: 270% of the area of the exposed primer; area of the exposed base metal <30%; 2 points: the area of the exposed primer <70%; area of the exposed base metal > 30% ^ &70; 70% 1 point: area of exposed primer 270%; area of exposed base metal > 70% coated adhesive member (mainly adhesive) Pre-coated in Examples 23 to 30 The steel sheet was coated with a melamine resin (Kansai; Amilac # 1〇〇〇) with a rod-shaped coating tool with a film thickness of 30 μm after drying, and was heated to 130 ° C in a heating furnace and dried for 20 minutes. minute. The steel sheet was allowed to stand overnight and then processed to an Erichsen 値 = 7 mm. Tape (Nichiban; CellotapeTM) is attached to the processing area i and is inclined at 45 degrees. Quickly remove the tape. The adhesiveness of the coating was evaluated in accordance with the percentage of peeled area in the following scoring standards. 5 points: no peeling 4 points: peeled area ratio < 5% 3 points: peeled area ratio 25%, < 30% 2 points: peeled area ratio 230%, < 50% 1 point: peeling area ratio 250% (secondary adhesion) Same as the main adhesion test, the surface of the steel sheet is covered with melamine tree 24 This paper is in accordance with China National Standard (CNS) A4 specifications ( 210 X 297 mm) (Please read the notes on the back before filling this page) Order --------- Line! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 555816 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (,) Allow to stand overnight. Each piece of steel was then placed in boiling water for 30 minutes and processed to an Erichsen 値 = 7 mm. Tape (Nichiban; Cellotape ™) is applied to the processing area, and the tape is quickly peeled off at an angle of 45 °. The adhesiveness of the coating was evaluated according to the percentage of peeled area in the following evaluation criteria. 5 points: no peeling 4 points: peeling area ratio < 5% 3 points: peeling area ratio, < 30% 2 points: peeling area ratio 230%, < 50% 1 point: peeling area ratio > 50% resistance Corrosive parts (2) (flat area) According to JIS Z 2317, the surface of the pre-coated steel sheet obtained in Examples 23 to 30 was sprayed with a 5% sodium chloride aqueous solution at a room temperature of 35 ° C, and a salt spray was performed. In the test, after the salt spray test was performed for 240 hours, the corrosion resistance was evaluated according to the proportion of white spots formed using the following scoring criteria. 5 points: no white spots 4 points: white spots < 10% 3 points: white spots 210%, < 20% 2: 2 points: white spots 220%, < 30% 1 point: white spots 230% (processed portion) In Example 23 The pre-coated steel sheet obtained to 30 is processed to an Erichsen 値 = 7mm, and then the room temperature is 25 in accordance with JIS Z 2317 (please read the precautions on the back before filling this page) -nn. ^ 1 ϋ ϋ -^-r ° J · ϋ ϋ ϋ n ϋ II n ϋ n I ϋ I ϋ n ϋ nn ϋ I n < This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 555816 A7- -—- ^ V. Description of the Invention (θ) At 35 ° C, a salt spray test is performed with a 5% sodium chloride aqueous solution. After 72 hours of the experiment, the corrosion resistance was evaluated according to the proportion of white spots formed using the following scoring criteria. 5 points: no white spots 4 points: white spots < 10% 3 points · white spots 210%, < 20% 2 points · white spots 220%, < 30% 1 point: white spots 230% rainbow fingerprint in Example 23 The pre-plated steel sheets obtained up to 26 were embossed on the coated surface with fingerprints, and were evaluated with the following scoring criteria according to the degree of fingerprints. 5 points: No identifiable fingerprint 4 points: Slightly identifiable fingerprints 3 points: Clear identifiable fingerprints 2 points: Obvious ft fingerprints 1 point z Very significant fingerprint lubricating parts use hydroforming with a conical punch The testing machine used the pre-plated steel sheets obtained in Examples 27 to 30 to perform a forming test at room temperature under the following conditions. The evaluation of lubricity is based on the degree of abrasion. Punch diameter: Φ70mm Blank diameter: Φ150mm Bias load: 5kg / cm² Forming speed · 3.3XHT2m / s 26 This paper size applies to Chinese National Standard (CNS) A4 specifications (210 x 297 mm) — (Please read the notes on the back before filling this page)

--------訂---------線L 經濟部智慧財產局員工消費合作社印製 555816 A7 B7 五、發明說明（一） 夾具：FCD — 500 當成形高度到達最大可成形高度的80%即完成成形加 工。以巨觀的方式評估擦傷的程度，並以下列評分標準評 估其結果。 5點：可成形，鋼材表面無瑕疵 4點：可成形，鋼材表面無瑕疵，有輕微的污點在滑移的 表面 3點：可成形，一些擦傷的痕跡在鋼材表面 2點：可成形，許多線狀擦傷的痕跡在鋼材表面 1點：不可成形 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 27 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）-------- Order --------- Line L Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 555816 A7 B7 V. Description of the invention (1) Fixture: FCD — 500 When the forming height reaches the maximum 80% of the forming height is completed. The extent of the abrasions was assessed in a grand view, and the results were evaluated using the following scoring criteria. 5 points: can be formed, the surface of the steel is flawless 4 points: can be formed, the surface of the steel is flawless, there are slight stains on the slippery surface 3 points: can be formed, some scratch marks are on the surface of the steel 2 points: can be formed, many The traces of linear abrasion are on the steel surface at 1 point: not formable (please read the precautions on the back before filling this page). Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 210 X 297 public love)

Claims (1)

555816 一_ A8 t . B8 」公告本 错 六、申請專利範圍 1·—種非鉻酸鹽金屬_表匣處理劑，其每一公升包括； (a) O.Oi至1〇〇克/升的矽烷聯結劑及/或其之水解的濃 縮產物， (b) 0.05至100克/升的可以水分散之二氧化矽（固體 )，和 (c) 0.01至50克/升之含锆離子之锆化合物及/或0.01 至50克/升之含鈦離子之鈦化合物，及/或 (d) 0.01至100克/升含硫羰基化合物及/或 (e) 0.1至100克/升之水溶性丙烯酸樹脂。 2. 如申請專利範圍第1項之非鉻酸鹽金屬表面處理劑 ，其包括〇.〇1至1〇〇克/升的磷酸鹽離子。 3. —種處理金屬表面的方法，其包括以根據申請專利 —-一·— 範圍第1或2項之金屬表面處理劑處理鋼材表面。 4·根據申請專利範圍第3項之處理金屬表面的方法， 其中該鋼材爲一種被覆金屬之鋼材。 5·—種根據申請專利範圍第3項之方法獲得之表面已 處理之鋼材。 6.—種根據申請專利範圍第4項之方法獲得之表面已 處理之被覆金屬的鋼材。 7· —種生產經被覆之鋼材的方法，其包括以根據申請 專利範圍第1或2項之金屬表面處理劑處理被覆金屬之鋼 材的表面，然後被覆在其頂部上。 8.—種根據申請專利範圍第7項之方法獲得之被覆鋼 材。 1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) tsj· 經濟部智慧財產局員工消費合作社印？π555816 A_A8 t. B8 "Announcement Wrong 6. Application for patent scope 1 · A kind of non-chromate metal_box treatment agent, each liter includes: (a) O.Oi to 100 g / L Silane coupling agent and / or its hydrolyzed concentrated product, (b) 0.05 to 100 g / L of water-dispersible silica (solid), and (c) 0.01 to 50 g / L of zirconium ion-containing Zirconium compounds and / or titanium compounds containing 0.01 to 50 g / L of titanium ions, and / or (d) 0.01 to 100 g / L of sulfur-containing carbonyl compounds and / or (e) 0.1 to 100 g / L of water solubility Acrylic. 2. The non-chromate metal surface treatment agent according to item 1 of the patent application scope, which comprises 0.001 to 100 g / L of phosphate ions. 3. A method for treating a metal surface, which comprises treating a steel surface with a metal surface treating agent according to the scope of claims 1 or 2 of the patent application. 4. The method for treating a metal surface according to item 3 of the scope of patent application, wherein the steel is a metal-coated steel. 5 · —A surface-treated steel obtained according to the method in item 3 of the scope of patent application. 6.—Steel material with surface-treated coated metal obtained by the method of item 4 of the scope of patent application. 7. A method of producing a coated steel material, which comprises treating the surface of the coated steel material with a metal surface treating agent according to item 1 or 2 of the scope of the patent application, and coating the surface of the coated steel material. 8.—A coated steel obtained by the method of item 7 of the scope of patent application. 1 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) tsj · Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs? π