經濟部中*樣车局貝工消費合作社印東 412600 A7 A7 _B7_ 五、發明说明（1 ) 發明所颶的技術領域 本發明係有關耐變黑性及耐白銹性優越的熔融鋅系電 鍍鋼板之表面處理方法。更詳細而言，本發明係令熔融鋅 系電鍍鋼板表面處理酸性水溶液，於短期間內去除已濃化 於該表面上的鋁或鉛，藉由施以塗布型鉻酸鹽處理，可提 高耐變黑性及耐白銹性，且酸性水溶液可經長期間保持著 初期性能，在不發生污泥下可連續使用的表面處理方法。 習知技術 · 鋼板之利用鑛辞處理的陽極保護（sacrificial protection )係最具效果且經濟的•故目前相當於在日本之 年間粗鋼生產量1億噸之1 0%的1 0 0 0萬噸係被生產 成鍍鋅鋼板，被廣泛使用於建材、汽車及家電等廣泛領域 。利用鋅之陽極保護，係鋅及鋼鐵之二種金屬在接觸的狀 況下，形成電極，較早的金屬之鋅成爲陽極，鐵則予以陰 極化，可抑制僅單獨鐵時之局部電池形成的陽極溶解，並 防止鋼鐵之腐蝕。因此，在與鋼鐵接觸的鋅消失的時刻， 防銹作用即結束，故欲使該作用效果可長期持續，即有抑 制鋅層之腐蝕的必要，乃於電鍍後施以鉻酸鹽處理作爲其 對應手段。 然而，利用此種鉻酸鹽處理之防銹方法有下述的問題 存在。 亦即，熔融鍍鋅系鋼板之利用鉻酸鹽處理可顯著的防 止白銹之發生，惟反之於庫存期間或輸送中卻會發生外觀 本纸張尺度速用中國國家揉率（CNS } A4洗格（210X297公釐） ^^1 ^^^1 *nl tn n ^^^1 tin ^^^1 ^^^1 mi、一WJ _ * {请先w讀背面之注意事項再填寫本頁) -4 - 經濟部中央樣率局負工消费合作社印装 412§00 A7 ___B7_ 五、發明説明（2 ) 上有問題之變黑現象。此現象在熔融鍍鋅後雖然進行表面 光軋延（skin pass rolling )，但鏡辞中含有鈴之溶融鍍鋅 鋼板，及含有數％之鋁之熔融鍍鋅鋁之鋼板之一者被發現 會較容易發生。此變黑係於鍍鋅表面之鋅（結晶）花（ spangle )中的某特定之結晶方位處特別有形成灰黑色之特 徵，因此以習知方法使鋅花減少化亦在某種程度上有效。 又於會發生變黑之鋅花內有鉛之粒子存在，此即形成活性 點而助長變黑現象。其對策若將鍍浴中的鉛設成極低鉛（ 0 . 0 1%以下）時，則較難變黑一事亦係習用公知的。 然而，於熔融鍍鋅鋼板方面•喜好鋅花之使用者亦多，於 鍍浴中添加鉛係不可避免的。再者•熔融鍍鋅鋁合金鋼板 係利用施行鉻酸鹽處理，由於該優越的耐蝕性，近年以在 無塗裝的狀態變成較多僅以裸露的被使用，然而鍍層中的 鋁濃度高，由於鋅及鋁之局部電池作用與一般的熔融鍍鋅 鋼板比較變黑現象係顯塞的被助長，乃損及商品價値。 然而，鍍鋅鋼板之變黑現象係與白銹相同之以（ Z n C 0 3 ) X · 〔Ζη (OH) 2〕y表示的鹸式碳酸鋅爲 在4 0 0〜7 0 0 nm之可見光波長領域的粒徑，故被視 爲光線容易引起散射與吸收以致可看見黑色。變黑係在氧 氣不足狀況下的腐蝕生成物，尤其可視作隨著來自粒界之 腐蝕進行而形成的。因此，由快速熔化（Hash )金屬在粒 界濃化的鉻化合物可抑制來自粒界之腐蝕，被視作有助於 防止黑銹發生。如此，在鉻酸鹽處理之前，由處理N i、 Co、 Fe等之快速熔化處理，對鍍鋅系鋼板之變黑問題 本紙張尺度逍用中88國家揉準（CNS > Α4規格U10 X 297公釐） --- ---1----- 装---u u J—訂 H * ' {請先Μ讀背面之注意事項再填寫本頁) -5 - 412600 A7 _____B7_ 五、發明説明（3 ) 可成爲有效的對策。 然而，在鉻酸鹽處理之前先實施日本特公平 3 — 4 9 9 8 2號公報所揭示的快速熔化處理可抑制變黑 現象，惟析出金靥附著量容易變成過多，由於在鍍鋅表面 上有不同種金屬附著無寧說明容易發生白銹之問題。 另一方面，於前述日本特公平3 — 5 2 5 4 6號公報 ’爲抑制F e等的過量析出，使含有鋁酸離子及/或鋅酸 離子，惟因係鹼性溶液使正溶解中的鋁或鋅以離子形式溶 存的量較少，隨著處理，氫氧化鋅或氫氧化鋁乃形成主體 之污泥而大量發生。因此配管或噴嘴生成阻塞，不僅管線 操作性上有困難，F e等的金屬離子亦同時共沈澱成污泥 ，變成未能獲得所期待的附著量，耐變黑性能會成爲不穩 定的* 發明欲解決的課題 ’ 經濟部中央梯準局貝工消費合作社印装 —：------^-----笨I nt ^^^1 Jn^^ ' (請先閲讀背面之注項再填寫本頁) 本發明之應解決的課題，係在於前述的習知技術之藉 由Ni、 Co、 Fe等快速熔化處理以抑制過量的重金屬 之附著，可同時滿足熔融鋅系電鍍鋼板之耐變黑性及耐白 銹性之二者，再者即使隨著處理而正溶解的鋅或鋁離子濃 度增加，伴隨污泥發生，此等重金屬離子不會共沈，可得 由建浴初期經長期間仍安定的性能，且欲提供不需污泥去 除作用之熔融鋅系電鍍鋼板之表面處理方法。 解決課題所採的手段 本紙張尺度遑用中困國家標準（CNS ) A4洗格( 210X297公釐） -6- κ 26〇〇 Α7 _Β7____ 五、發明説明（4 ) 本發明人等，爲解決前述的習知技術之問題，乃著眼 於曰本特開平6 — 2 9 3 9 7 3號公報所掲示的酸性取代 電鍍液係於酸性水溶液中可捕捉利用硫酸正溶解的Ζ η離 子或A 1離子，故經長期間不發生污染，可保持其初期性 能之特性。此先行技術之酸性取代電鍍液係因N i、C 〇 、Fe等重金屬於短時間內有效的折出之故，如前述般， 由於重金靥過量析出使耐白銹性容易降低》因此在短時間 內若使微量之重金臈析出時，則熔融鋅系電鍍鋼板之表面 狀態容易形成不均勻，尤其對含有高鋁之熔融鋅系電鍍鋼 板之變黑防止效果會缺乏。 因此，經各種檢討，結果藉由於酸性取代電鍍液添加 事先使取代電鍍性降低的鋅離子或鋁離子，發現使建浴初 期之Fe， Co、 Ni之重金屬析出量可予抑制。In the Ministry of Economic Affairs * Sample Vehicle Bureau, Shellfish Consumer Cooperative, Indo 412600 A7 A7 _B7_ V. Description of the Invention (1) Technical Field of the Invention The present invention relates to a molten zinc-based electroplated steel sheet excellent in blackening resistance and white rust resistance. Surface treatment method. More specifically, in the present invention, the surface of a molten zinc-based electroplated steel sheet is treated with an acidic aqueous solution, and aluminum or lead that has been concentrated on the surface is removed in a short period of time. By applying a coating chromate treatment, the resistance can be improved. Surface treatment method that has blackening and white rust resistance, and that the acidic aqueous solution can maintain initial performance for a long period of time, and can be used continuously without sludge. Known technology · The anodic protection of steel plates is the most effective and economical. Therefore, it is currently equivalent to 10% of 10 million tons of 100 million tons of crude steel production in Japan. It is produced into galvanized steel sheet, which is widely used in a wide range of fields such as building materials, automobiles and home appliances. Utilizing anodic protection of zinc, two kinds of metals, zinc and steel, form electrodes under the condition of contact. The zinc of the earlier metal becomes the anode, and iron is anodized, which can suppress the anode formed by the local battery when only iron is used alone. Dissolves and prevents corrosion of steel. Therefore, at the moment when zinc in contact with iron and steel disappears, the rust prevention effect is ended. Therefore, in order to make the effect last long, that is, it is necessary to suppress the corrosion of the zinc layer, a chromate treatment is applied after plating. Corresponding means. However, the rust prevention method using such a chromate treatment has the following problems. That is, the use of chromate treatment of the hot-dip galvanized steel sheet can significantly prevent the occurrence of white rust, but the appearance will occur during the inventory period or during the transportation. This paper scale uses the Chinese national kneading rate (CNS} A4 washing Grid (210X297 mm) ^^ 1 ^^^ 1 * nl tn n ^^^ 1 tin ^^^ 1 ^^^ 1 mi, a WJ _ * {Please read the precautions on the back before filling this page) -4-Printed 412 §00 A7 ___B7_ by the Central Sample Rate Bureau of the Ministry of Economic Affairs, Consumer Cooperatives V. The blackening phenomenon in the description of the invention (2). Although this phenomenon has undergone skin pass rolling after hot-dip galvanizing, one of the hot-dip galvanized steel sheets containing Suzuki and one of the hot-dip galvanized aluminum sheets containing several percent of aluminum was found to be less effective than hot-dip galvanizing. Easy to happen. This blackening is a characteristic of forming a gray-black color at a specific crystal orientation in the zinc (crystal) flower (spangle) on the galvanized surface, so reducing the zinc flower by conventional methods is also effective to a certain extent . In addition, there will be lead particles in the zinc flower that will turn black. This will form an active point and promote the blackening phenomenon. As for the countermeasures, if the lead in the plating bath is set to be extremely low (less than 0.01%), it is difficult to turn black, which is also a well-known practice. However, in terms of hot-dip galvanized steel sheet, there are also many users who like zinc flowers. Adding lead to the plating bath is inevitable. Furthermore, the hot-dip galvanized aluminum alloy steel sheet is treated with chromate. Due to the excellent corrosion resistance, it has been used more in the uncoated state in recent years, and it is only used in bare. However, the aluminum concentration in the coating is high. Due to the local battery effect of zinc and aluminum compared with the general hot-dip galvanized steel sheet, the phenomenon of blackening is significantly promoted, which is harmful to the commodity price. However, the blackening phenomenon of galvanized steel sheet is the same as that of white rust. The zinc zinc carbonate represented by (Z n C 0 3) X · [Zη (OH) 2] y is in the range of 4 0 ~ 7 0 0 nm. The particle size in the visible wavelength range is considered to be the light that easily causes scattering and absorption so that black is visible. The corrosion products of the blackening system under the condition of insufficient oxygen can be regarded as being formed as the corrosion from the grain boundary progresses. Therefore, the chromium compound concentrated in the grain boundary by a fast-melting (Hash) metal can suppress the corrosion from the grain boundary and is considered to help prevent the occurrence of black rust. In this way, before the chromate treatment, the rapid melting treatment of Ni, Co, Fe, etc. was applied to the blackening of galvanized steel sheets. This paper is standard in 88 countries (CNS > Α4 size U10 X 297 mm) --- --- 1 ----- equipment --- uu J-order H * '{Please read the precautions on the back before filling this page) -5-412600 A7 _____B7_ V. Invention Explanation (3) can be an effective countermeasure. However, prior to the chromate treatment, the rapid melting treatment disclosed in Japanese Patent Publication No. 3-4 9 9 8 2 can suppress the phenomenon of blackening, but the amount of deposited gold tincture tends to become excessive. There are different kinds of metal adhesion, which indicates that white rust is prone to occur. On the other hand, in the aforementioned Japanese Patent Publication No. 3-5 2 5 4 6 ', in order to suppress excessive precipitation of Fe and the like, aluminate ions and / or zincate ions are contained, but they are being dissolved in an alkaline solution. The amount of aluminum or zinc dissolved in ionic form is small, and with treatment, zinc hydroxide or aluminum hydroxide is a large amount of sludge that forms the main body. Therefore, piping or nozzles become clogged, which not only has difficulty in the operability of the pipeline, but also metal ions such as Fe co-precipitate into sludge at the same time, failing to obtain the desired adhesion amount, and the blackening resistance will become unstable. * Invention Issues to be solved 'Printed by the Shellfish Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China ———-------- ^ ----- Stupid I nt ^^^ 1 Jn ^^' (Please read the note on the back first (Please fill in this page again) The problem to be solved by the present invention lies in the aforementioned conventional technology, which uses Ni, Co, Fe and other rapid melting treatments to suppress the adhesion of excessive heavy metals, and can simultaneously meet the resistance of molten zinc-based electroplated steel plates. Both blackening and white rust resistance, and even if the concentration of the zinc or aluminum ions that are being dissolved increases with the treatment, with the occurrence of sludge, these heavy metal ions will not co-sink. It has stable performance for a long period of time, and it is intended to provide a surface treatment method of molten zinc-based electroplated steel sheet without the need for sludge removal. Means adopted to solve the problem The paper standard uses the National Standard for the Difficulties (CNS) A4 Washer (210X297 mm) -6- κ 26〇〇Α7 _Β7 ____ 5. Description of the Invention (4) The inventors, etc., in order to solve the aforementioned problems The problem of the conventional technology is focused on the acidic substitution plating solution disclosed in Japanese Patent Application Laid-Open No. 6 — 2 9 3 9 7 3 in an acidic aqueous solution, which can capture Zn ions or A 1 ions that are dissolved by sulfuric acid. Therefore, no pollution occurs over a long period of time, and the characteristics of its initial performance can be maintained. The acidic replacement electroplating solution of this prior art is because heavy metals such as Ni, Co, and Fe are effectively removed in a short period of time. As mentioned above, due to the excessive precipitation of heavy metals, the white rust resistance is easily reduced. If a small amount of heavy gold is precipitated within a period of time, the surface state of the molten zinc-based electroplated steel sheet is likely to be uneven, and particularly, the effect of preventing blackening of the molten zinc-based electroplated steel sheet containing high aluminum is lacking. Therefore, after various reviews, it was found that the addition of zinc ions or aluminum ions that had previously lowered the plating performance of the plating solution due to the acidic substitution plating solution, found that the precipitation of heavy metals such as Fe, Co, and Ni at the initial stage of the bath was suppressed.
經濟部中央揉率局貝工洧费合作社印I n —II I —^1 _ _ F (請先聞讀背面之注意事項再填寫本頁) 再者，由於連續作業而由熔融鋅系電鍍鋼板表面熔解 的鋅或鋁離子係於添加硫酸而以硫酸鹽方式予以捕捉，惟 隨著該情形，蝕刻量降低，耐變黑性會成爲容易降低。因 此於本酸性水溶液中，使含有氟化氫所代表的氟化物，再 者若亦合併使用具有p Η之緩衝機能之磷酸時，則發現鋅 系電鍍鋼板表面，尤其可助長該氧化被膜之溶解促進作用 « 本發明人等經精心檢討的結果，乃確立藉由限定有助 於蝕刻之成分量，調整pH於1 . 5〜4 . 5，亦即可以 簡單的管線維持管理使具有足夠的變黑及白銹防止性之熔 融鋅系電鍍鋼板穩定並能工業規模的製造方法，以至達成 本紙張尺度逍用中Η困家揉準（ CNS ) A4規格（210X297公嫠) ^ 6 Ο Ο Α7 _____Β7_ 五、發明説明（5 ) 初期的效果。 亦即，本發明係提供於鋅或鋅合金系之已施以熔融電 鍍的熔融鋅系電鍍鋼板表面上，以含有由鐵、鈷、鎳選出 的至少一種之重金屬離子，事先添加有鋅離子及/或鋁離 子之pH 1 . 5〜4 , 5之酸性水溶液處理，經水洗後 *施以塗布型鉻酸鹽處理爲特徵之熔融鋅系電鍍鋼板之表 面處理方法》 又，前述酸性水溶液，係以含有1〜2 0 0 g/<之 硫酸離子，0 . 3〜3g/i之磷酸離子，0 . 3〜3g 之氟離子，1〜15g/^之有機酸，0 · 05〜5 g/<之由鐵、鎳、鈷選出的至少一種重金屬離子，含有 可控制該重金屬離子之朝向前述熔融鋅系電鍍鋼板表面的 過量析出之1〜5 0 g 之鋅離子及/或鋁離子，經予 調整成pH 1.5〜4.5的酸性水溶液爲宜》 以下，詳細說明本_明之內容。 於本發明，熔融鋅系電鍍鋼板並未予特別限定，惟可 舉出有：含有A 1 0 . 1〜0 . 3%之一般的熔融鍍鋅 經濟部中央揉準扃貞工消费合作社印装 [---^-----策---- Ϊ I Ji 一^ (請先閲讀背面之注意事項再填寫本頁> 鋼板，及以相同A 1量含有Pb 0 . 05〜0 · 3%之 熔融鍍鋅鋼板，含有A1 0.3〜6%，微量的La、 Ce、Mg等之熔融鋅鋁合金電鍍鋼板。 本發明之酸性水溶液係含有以下的成分。 首先，於酸性水溶液內在處理前事先添加鋅離子及/ 或鋁離子。該離子之添加量以1〜5 Og/^爲宜。添加 的鋅離子或鋁離子以採用此等的硫酸鹽.、磷酸鹽、硝酸鹽 本紙張尺度逍用中國困家標準（CNS ) A4規格（210X297公釐） -8- 經濟部t央樣率局貝工消费合作社印製 412600 A7 _B7_五、發明説明（6 ) 、碳酸鹽、氧化物、氫氧化物或有機酸鹽等爲宜。氯化物 在長期使用的情形，氯離子會累積·有引起電鍍裝置之腐 蝕的危險性，故並不合適。再者’該離子之含有量未滿1 g/<時，鈷、鎳之重金屬離子會容易的過量析出，招致 耐白銹性之降低，若超過5 0 g/ <時’則其效果飽和’ 僅經濟上的損失會變大而已。 硫酸離子雖係由硫酸所洪給，惟此係爲捕捉由熔融鋅 系電鍍鋼板溶解的鋅離子或鋁離子而隨著此等離子之增加 而予補給，逐漸增加。因此，硫酸離子量係由蝕刻量及電 鏟液之共同負擔量予以決定，惟一般係在1〜2 0 0 g/ 之之範圍。未滿1 g/ <時雖可捕捉正溶解的鋅離子或鋁 離子但並不足夠：若超過2 0 0 時，在短時間內之 鋁去除效果會降低，若未能充分進行其後的水洗時，則硫 酸離子會大量殘留於電鍍表面上，使耐白銹性降低並不合 適· 磷酸離子以採用原磷酸爲宜。使含於酸性水溶液中的 磷酸離子量爲0 . 3〜3g/<。未滿0 . 3g/<時， 在鋅離子或鋁離子之已增加的情形，不僅會損及鋁去除效 果，對有機酸量較少的情形，pH緩衝能力會降低，pH 變成容易急速上升•以致影響至成分均衡，若超過3 g/ <時，則由於蝕刻量會增加，故鐵、鎳、鈷之重金屬離子 變成容易析出，使耐白銹性降低。 至於氟離子，可由自氟化氫酸、矽氟化氫酸選出的至 少一種予以供給，含於酸性水溶液中的氟離子量爲0.3 I- ^^1 - - ^^1 —ϋ ί n ^^1 - ml· In ^-* {锖先聞婧背面之注意事項再填寫本頁) 本纸張尺度遑用中HB家標準（CNS ) A4规格（210X297公釐） -9- Α7 Β7 五、發明説明（7 ) 〜3g/<。未滿〇 . 3@/<時，鋅離子或鋁離子會增 加的情形，在短期間內的鋁去除效果會受損，若超過3 g 時，則由於蝕刻量會增加，鐵、鈷、鎳之重金屬離子 變成容易析出，不僅耐蝕刻性會降低，被保持在低pH領 域之情形，即使爲不銹鋼製裝置亦變成容易引起裝置腐蝕 ，並不合適。 至於有機酸，係由自羥基乙酸、乳酸、蘋果酸、酒石 酸、檸檬酸，葡糖酸、抗壞血酸而成之群體選出的至少一 種予以供給》含有有機酸量須爲1〜1 5· g / <。有機酸 量未滿1 g/《時pH緩衝能力會降低，藉由硫酸補給量 變多，使P Η成爲下限以下，引起裝置腐蝕之危險性。若 超過1 5 g/<時，則其效果會飽和，經濟上的損失會變 大。 經濟部中央揉準局負工消费合作社印袋 (請先閲讀背面之注意事項再填窝本頁) 本發明之酸性水溶液係因以含有鐵、鈷、鎳之中之一 種或二種以上的重金屬離子可促進短期間內的蝕刻，用作 取代電鍍原理之初期反應的蝕刻助劑效果成分係必要的》 爲供給該重金屬離子，以採用該重金饜之硫酸鹽、磷酸鹽 、硝酸鹽、碳酸鹽、氧化物、氫氧化物或有機酸鹽等爲宜 。氯化物在長期使用的情形，因氯離子會累積有引起裝置 腐蝕之危險性故並不適宜。 本發明之酸性水溶液所含_有的重金靥離子量，以金屬 換算爲0 . 05〜，較宜爲0 · 1〜1 ♦ 5g/ 《。未滿0 . 05g/<時，未能獲得所期待的蝕刻效果 ，超過5 g/ <時，則金屬析出量容易形成過量而未能進 本纸張尺度通用中國國家揉率（CNS > Α4规格（2丨0X297公釐） -10- Α7 ___ _Β7___ 五、發明説明（8 ) 行管線控制。 又，相對於在酸性水溶液之此種金靥之中以鈷及鎳之 電位約略相同電位，鐵則電位差稍大》因此有電位差之二 種金屬，亦即若使鐵離子與鈷離子、鐵離子與鎳離子之組 合共存時，則取代反應可予活性化|在防止大量的鋅離子 或鋁離子混入時之反應性降低方面有效果，同時對鐵化合 物係較鈷或鎳化合物可予價廉的大量消費的鋼鐵製造廠商 之生產線上而言，成本優點方面較大。 具有上述成分組成之本發明之酸性水溶液之p Η係予 調整於1.5〜4.5之範圍內，惟對pH較低的情形， 添加鋅或鋁氧化物，或氨予以調整亦可•將p Η範圍限定 於1 . 5〜4 _ 5係意指在pH未滿1 . 5時含有過量的 無機酸，僅蝕刻量變多，又再者若成低p Η時，則因有引 起裝置腐蝕之問題的危險性，故不合適。另一方面，藉由 補給以硫酸爲主劑之補給劑，p H並無超過4 · 5之情形 ，惟若未能補給時P Η會上升，於處理液中變成容易生成 污泥*並不適合所致。 經濟部中央橾準局負工消費合作杜印装 (請先閾讀背面之注意事項再填窝本頁) 如此藉由將pH已予調整成1.5〜4.5之水溶液 噴霧或浸漬處理至熔融鋅系電鍍鋼板表面上使與酸性水溶 液接觸，水洗後，若予乾燥即可。 酸性水溶液之溫度爲室溫〜8 0°C，處理時間在1 5 秒以下即足夠，至於析出的重金屬若未滿5mg/ma時， 在不使耐白銹性降低下可使變黑抑制效果滿足。對未設定 下限析出量係如前述般，若能使處理液組成保持於本發明 本纸張尺度读用中«國家揉車（CNS ) A4规格（210X297公釐） -11 - 4?3600 A7 ___B7__ 五、發明説明（9 ) 之範圍內時·即或重金屬析出量爲〇mg/ml時，已於最 表層濃化的鋁或鉛量會降低*可使變黑抑制效果發揮所致 。另一方面，若在5 mg /m1以上時，則因耐白銹性會降 低，並不合適。 水洗係爲避免酸性水溶液成分之進入其後施加的塗布 型鉻酸鹽處理液內，以稀釋倍率5 0 0倍以上的水質進行 水洗爲宜。 乾燥係以水分可予去除的程度即可，板溫以在5 0〜 lOOt之範圍爲較普遍的。 熔融鋅系電鍍鋼板係以以上的酸性水溶液處理表面後 ，施以塗布型鉻酸鹽處理，不進行水洗下予以乾燥。塗布 型鉻酸鹽處理條件並無特別限定的必要，若以公知的鉻酸 鹽處理方法使附著5〜1 0 Omg/πί即可。 如前述般，鎳、鈷、鐵之快速熔化處理，係用作熔融 鋅系電鍍鋼板之變黑抑制手段之有力的方法，惟此等重金 屬若過量析出時，則耐白銹性會惡劣。 經濟部中央榣率.局貝工消费合作社印装 ^^1 n - —ί ^^1 ^^1· I J木 _ =1 m ^^1 ^^1 J^i - . (请先M讀背面之注意事項再填寫本頁) 因此本發明人等對最容易變黑的熔融鋅- 5 %鋁合金 電鍍鋼板採用日本特開平6 — 2 9 3 9 7 3號公報所揭示 的酸性取代電鍍液進行各種檢討的結果，若能事先令使取 代電鍍性降低的鋅離子或鋁離子時，則可確認出可抑制重 金餍之過量析出。又，以於日本特開平6—293973 號公報揭示的酸性取代電鍍液進行短期間處理時，可抑制 重金屬過量析出，在不使耐白銹性降低下可處理.但成爲 耐變黑性低劣的結果》 本紙張尺度逍用中困围家標率{ CNS ) A4规格（210X297公釐） -12- 412600 A7 B7 經濟部中央橾準局負工消费合作杜印装 五 、發明説明 I ( 10) 因此 若 比 較解 析 該 電 鍍 鋼 板 之 最 表 面 時 f 以 後 者 的 方 法 所 處理 的 鋁 濃化 度係 較 以 ^ * 刖 者處 理 者 爲 高 — 事 可 由 X 射 線光 電子 分 光 法（ X P S ) 等 最 新 的 分 析 機 器 予 以 碓 認 9 亦 即 ，熔 融鋅 -5 % 鋁 合 金 電 鍍 Aim 鋼 板 之 變 黑 現 象 係 利 用 於 電鍍 最表 層 之 已濃 化 的 鋁 之 去 除 程度 所 影 響 者 乃 係 顯 而 可 知 的 。又 對 一 般的 熔 融 鍍鋅 鋼 板 亦 可 發 現 同 樣 的 電 鍍 最 表 層 之 鋁之 去 除 程度 上有 不 同 〇 且 9 即 使在 螢 光 X 射 線 分 析 裝 置 (X R F )- 鋁 強 度 係 分析 深 度 約 1 β 之 故 » 由 於 達 熔 融 鋅系 電 鍍 鋼板 之 電 鍍 層 與 鋼 板 界 面 上 存在 的 鋁 富 化 層 爲 止 並未 測 定 ，故 可 簡 單 以 A 1 之 強 度 觀 察 絕 濃 化 度 上 的 不 同 〇 • 以下 記 載 的A 1 強 度 係 以 利 用 螢 光 X 射 線 分析 裝 置 之 強 度 (k C P s ) 表 示 成 鋁 濃 化 度 之 不 同 〇 因 此 若使含有 以 酸性且 鋁 之 溶解 能 力 最 高 的 氟 化 氫 酸 之 酸性 裝 置 用 電 鍍 液進 行短 期 間處理 時 則 即 使 鐵 鈷 X 鎳 等 重 金 屬 析出 量 未 滿 0〜 0 * 3 m g / m* 若 A 1 強 度 成 爲 某値 以 下 時 > 發現 出可發揮 變黑抑制功能 〇 亦即 A 1強 度 係 依 所 用 的 螢 光 X 射 線 分 析 裝 置 不 同 而 數 値有 不 同 ，惟 依 本 發 明 人 等 所 使 用 的 螢 光 X 射 線 分析 裝 置 之熔 融 鋅 一 5 % 鋁 合 金 電 鍍 鋼 板 之 情 形 對 jtrrf 無 處 理 之 表 示 出3 0 3 5 k C P S 之 A 1 強 度 1 而 被 認 爲 耐 變 黑 性 上 有效 果 的 A 1 強 度 則 在 2 0 k C P S 以 下 又 一 ήη. WL 的 熔 融鍍鋅 之 情形 > 對 無處 理 者 爲 3 4 k C P S ♦ 而 處 理 後則爲 2 k c p s以下 〇 寫 本 頁 衮 訂 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 请 先 閱 讀 背 A 之 注 意 事 項 再 -13- 奶600 A7 _B7___ 五、發明説明（11) 因此，於抑制熔融鋅系電鍍鋼板之變黑現象上若能使 電鍍最表層之已濃化的A 1量降低時即可，惟將作爲有助 於酸性水溶液中的蝕刻之磷酸離子及氟離子、鋅離子或鋁 離子之捕捉劑亦可作用的硫酸離子，亦具有pH緩衝機能 之有機酸離子，及用作取代電鍍反應蝕刻助劑機能的鎳、 鈷、鐵離子之含有量，限定於特定範圍內，藉由調整pH 成1 . 5〜4 . 5，鋅離子或鋁離子不致大量累積，經長 期間不發生污泥且可繼續使用，乃係由本發明人所發現的Printed by the Central Government Bureau of the Ministry of Economic Affairs, Cooperatives, I n —II I — ^ 1 _ _ F (please read the precautions on the back before filling out this page). Furthermore, the molten zinc-based electroplated steel sheet is used for continuous operation. Zinc or aluminum ions that are melted on the surface are trapped as sulfuric acid by adding sulfuric acid. However, in this case, the amount of etching is reduced and the blackening resistance is easily reduced. Therefore, in this acidic aqueous solution, if the fluoride represented by hydrogen fluoride is contained, and if phosphoric acid having a buffer function of pp is also used in combination, it is found that the surface of the zinc-based electroplated steel sheet can particularly promote the dissolution promoting effect of the oxide film. «As a result of careful review by the present inventors, it was established that by limiting the amount of components that contribute to the etching, the pH was adjusted to 1.5 to 4.5, that is, the simple pipeline maintenance and management can be made to have sufficient blackening and The white rust preventive molten zinc-based electroplated steel sheet is stable and can be manufactured on an industrial scale, reaching the cost of paper scale (CNS) A4 specification (210X297 cm) ^ 6 Ο Ο Α7 _____ Β7_ V. Description of the Invention (5) Initial effects. That is, the present invention is to provide zinc or zinc alloy-based molten zinc-plated steel plate surface which has been subjected to hot-dip electroplating, and in advance, zinc ion and a heavy metal ion containing at least one selected from iron, cobalt, and nickel are added. Surface treatment method of molten zinc-based electroplated steel plate characterized by coating with chromate treatment after washing with water and acidic aqueous solution of aluminum ion pH 1.5 ~ 4,5. With 1 ~ 2 0 0 g / < sulfate ion, 0.3 ~ 3 g / i phosphate ion, 0.3 ~ 3 g fluoride ion, 1 ~ 15 g / ^ organic acid, 0 · 05 ~ 5 g / < at least one heavy metal ion selected from iron, nickel, and cobalt, containing 1 to 50 g of zinc ions and / or aluminum ions which can be excessively deposited toward the surface of the aforementioned molten zinc-based electroplated steel plate to control the heavy metal ions, The acidic aqueous solution is preferably adjusted to a pH of 1.5 to 4.5. The content of this specification is explained in detail below. In the present invention, the molten zinc-based electroplated steel sheet is not particularly limited, but examples include: ordinary hot-dip galvanizing, which contains A 1 0.1 to 0.3%, printed by the Central Ministry of Economic Affairs and Consumer Cooperatives [--- ^ ----- 策 ---- Ϊ I Ji 一 ^ (Please read the precautions on the back before filling out this page > steel plate, and the same amount of A 1 contains Pb 0. 05 ~ 0 · A 3% hot-dip galvanized steel sheet containing 0.3 to 6% of A1, a small amount of La, Ce, Mg, and other molten zinc-aluminum alloy plated steel sheets. The acidic aqueous solution of the present invention contains the following components. First, the acidic aqueous solution is treated before Zinc ions and / or aluminum ions are added in advance. The amount of the ions is preferably 1 ~ 5 Og / ^. The added zinc ions or aluminum ions are to adopt these sulfates. Printed in accordance with the Chinese Standard for Household Standards (CNS) A4 (210X297 mm) -8- Printed by the Shell Sample Consumer Cooperative of the Central Sample Rate Bureau of the Ministry of Economic Affairs 412600 A7 _B7_ V. Description of the Invention (6), carbonates, oxides, hydrogen Oxides or organic acid salts are preferred. Chloride ions can accumulate and cause electroplating when chloride is used for a long time. It is not suitable because of the risk of corrosion. Furthermore, when the content of the ions is less than 1 g / <, the heavy metal ions of cobalt and nickel will be easily excessively precipitated, causing a reduction in white rust resistance. When it exceeds 50 g / < 'the effect is saturated', only the economic loss will increase. Although the sulfuric acid ions are supplied by sulfuric acid, this is to capture zinc ions dissolved by molten zinc-based electroplated steel or Aluminum ions are replenished with the increase of these ions and gradually increase. Therefore, the amount of sulfuric acid ions is determined by the amount of etching and the common burden of the electric shovel fluid, but it is generally in the range of 1 ~ 200 g / When it is less than 1 g /, it is not enough to capture the dissolved zinc ions or aluminum ions. If it exceeds 200, the aluminum removal effect will be reduced in a short time. When washed with water, a large amount of sulfuric acid ions remain on the plating surface, which is not suitable for reducing white rust resistance. Orthophosphoric acid is preferably used as the phosphate ion. The amount of phosphate ion contained in the acidic aqueous solution is 0.3 to 3g. / <. When less than 0.3 g / < The increase of aluminum ions not only impairs the aluminum removal effect, but also reduces the pH buffering capacity and the pH will increase rapidly when the amount of organic acid is small. As a result, the composition balance will be affected. If it exceeds 3 g / < At this time, since the amount of etching will increase, heavy metal ions of iron, nickel, and cobalt will be easily precipitated, which will reduce the white rust resistance. As for the fluoride ion, it can be supplied by at least one selected from hydrofluoric acid and silicon hydrofluoric acid, and contained The amount of fluoride ions in the acidic aqueous solution is 0.3 I- ^^ 1--^^ 1 —ϋ ί n ^^ 1-ml · In ^-* {锖 Notes on the back of Wen Jing before filling this page) This paper The standard used in the standard HB home standard (CNS) A4 (210X297 mm) -9- Α7 Β7 5. Description of the invention (7) ~ 3g / <. When it is less than 0.3@/< ;, zinc ions or aluminum ions will increase, and the aluminum removal effect will be impaired in a short period of time. If it exceeds 3 g, the etching amount will increase, and iron, cobalt, The heavy metal ions of nickel tend to be precipitated, not only the etching resistance is lowered, but they are kept in a low pH range. Even stainless steel devices are prone to cause corrosion of the devices, which is not suitable. As for the organic acid, at least one selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, and ascorbic acid is supplied. The content of organic acids must be 1 ~ 1 5 · g / <;. When the amount of organic acid is less than 1 g / min, the pH buffering capacity will decrease. As the amount of sulfuric acid replenishes, P Η will fall below the lower limit, causing the risk of corrosion of the device. If it exceeds 15 g / <, the effect will be saturated and the economic loss will increase. Printed bags for the Consumers' Cooperatives of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The acidic aqueous solution of the present invention contains one or two or more heavy metals of iron, cobalt, and nickel. Ions can promote etching in a short period of time, and the etch aid used to replace the initial reaction of the electroplating principle is an essential component. To supply the heavy metal ions, the sulfate, phosphate, nitrate, and carbonate of the heavy metal are used. , Oxides, hydroxides or organic acid salts are preferred. In the case of long-term use of chlorides, chloride ions can accumulate and cause the risk of corrosion of the device, which is not suitable. The amount of heavy metal sulfonium ions contained in the acidic aqueous solution of the present invention is 0.05 to 0.005 in terms of metal conversion, and more preferably 0 · 1 to 1 ♦ 5g /. When it is less than 0.05 g / <, the desired etching effect is not obtained. When it is more than 5 g / <, the amount of metal precipitation is likely to be excessive and fails to enter the paper scale. General China National Kneading Rate (CNS & gt Α4 specifications (2 丨 0X297mm) -10- Α7 ___ _B7___ V. Description of the invention (8) Line control. Also, the potential of cobalt and nickel is about the same potential as that of the gold tincture in acid aqueous solution. "Iron, the potential difference is slightly larger" Therefore there are two metals with potential difference, that is, if the combination of iron ions and cobalt ions, iron ions and nickel ions coexist, the substitution reaction can be activated | In preventing a large number of zinc ions or It is effective in reducing the reactivity when aluminum ions are mixed in. At the same time, the iron compound is more cost-effective in the production line of iron and steel manufacturers than cobalt or nickel compounds. It has a large cost advantage. The p Η of the acidic aqueous solution of the present invention is adjusted in the range of 1.5 to 4.5, but in the case of lower pH, it can be adjusted by adding zinc or aluminum oxide, or ammonia. • The range of p Η is limited to 1.5 ~ 4 _ 5 It means that when the pH is less than 1.5, an excessive amount of inorganic acid is contained, only the amount of etching is increased, and if it is low p Η, there is a risk of causing corrosion of the device, so it is not suitable. By supplementing with a sulfuric acid-based supplement, p H does not exceed 4 · 5, but P 上升 will rise if it is not replenished, and it becomes prone to produce sludge * in the treatment solution, which is not suitable. Du Yinzhuang, responsible for work and consumer cooperation of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) So by spraying or dipping the aqueous solution whose pH has been adjusted to 1.5 ~ 4.5 to the molten zinc system The surface of the plated steel sheet is brought into contact with an acidic aqueous solution, and it may be dried after washing. The temperature of the acidic aqueous solution is from room temperature to 80 ° C, and the processing time is less than 15 seconds. It is sufficient that the precipitated heavy metal is less than 5mg. At / ma, the blackening suppression effect can be satisfied without reducing the white rust resistance. For the non-set lower limit precipitation amount is as described above, if the composition of the treatment liquid can be maintained in the reading of the paper size of the present invention « National Kneading Car (CNS) A4 Specification (210X297 mm -11-4? 3600 A7 ___B7__ 5. When the invention description (9) is within the range, that is, when the amount of heavy metal precipitation is 0mg / ml, the amount of aluminum or lead that has been concentrated in the top layer will be reduced * It can turn black The inhibitory effect is exerted. On the other hand, if it is 5 mg / m1 or more, the white rust resistance is reduced and it is not suitable. The water-washing system is a coating type chromate that is applied to prevent the acidic aqueous solution components from entering. It is advisable to perform water washing in the treatment solution with water having a dilution rate of 500 times or more. Drying can be performed to the extent that moisture can be removed, and the board temperature is generally in the range of 50 to 100t. After the surface of the molten zinc-based electroplated steel sheet is treated with the above acidic aqueous solution, it is coated with a chromate treatment and dried without washing with water. The coating chromate treatment conditions are not particularly limited, and they may be adhered by 5 to 10 Omg / πί by a known chromate treatment method. As mentioned above, the rapid melting treatment of nickel, cobalt, and iron is a powerful method for suppressing the blackening of molten zinc-based electroplated steel sheets. However, if these heavy metals are excessively precipitated, the white rust resistance may be poor. Printed by the Central Government of the Ministry of Economic Affairs. Bureau Shellfish Consumer Cooperatives ^^ 1 n-— ^ ^ 1 ^^ 1 · IJ 木 _ = 1 m ^^ 1 ^^ 1 J ^ i-. (Please read the back first Please pay attention to this page and fill in this page) Therefore, the inventors have used the acid-substituted plating solution disclosed in Japanese Patent Application Laid-Open No. 6-2 9 3 9 7 for molten zinc-5% aluminum alloy plated steel plate that is most likely to turn black. As a result of various reviews, if zinc ions or aluminum ions that reduce the plating performance of the substitution can be ordered in advance, it can be confirmed that excessive precipitation of heavy metals can be suppressed. In addition, when the acid-substituted electroplating solution disclosed in Japanese Patent Application Laid-Open No. 6-293973 is processed for a short period of time, excessive precipitation of heavy metals can be suppressed, and it can be processed without reducing white rust resistance. However, it has poor blackening resistance. Result》 The standard of this paper is not easy to use. The standard of the house is {CNS) A4 size (210X297mm) -12- 412600 A7 B7 Duplicate work and consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention I (10) Therefore, if the outermost surface of the electroplated steel sheet is comparatively analyzed, the aluminum concentration processed by the latter method is higher than that of the ^ * one, which can be treated by the latest analysis equipment such as X-ray photoelectron spectroscopy (XPS). It is recognized that 9 is that the blackening phenomenon of the molten zinc -5% aluminum alloy plated Aim steel plate is affected by the degree of removal of the thickened aluminum used in the plating of the outermost layer. It is also found that the degree of removal of aluminum in the same electroplated outermost layer is different for ordinary hot-dip galvanized steel sheets. 9 Even in a fluorescent X-ray analysis device (XRF)-the strength of aluminum is about 1 β. » Since the aluminum-rich layer at the interface between the electroplated layer of the molten zinc-based galvanized steel sheet and the steel sheet has not been measured, the difference in absolute concentration can be easily observed at the strength of A 1. A 1 strength system described below The intensity (k CP s) of a fluorescent X-ray analyzer is used to indicate the difference in aluminum concentration. Therefore, if a short-term treatment is performed on an electroplating solution for an acidic device containing a hydrofluoric acid that is acidic and has the highest aluminum dissolving ability, Even if the amount of precipitation of heavy metals such as iron-cobalt X nickel is less than 0 to 0 * 3 mg / m * when the intensity of A 1 is less than or equal to 値, it is found that the blackening suppression function can be exhibited. That is, A 1 is strong. The number varies depending on the fluorescent X-ray analysis device used, but the indication of jtrrf without treatment depends on the situation of the molten zinc-5% aluminum alloy electroplated steel plate of the fluorescent X-ray analysis device used by the inventors and others. The A 1 strength of 3 0 3 5 k CPS and the strength of A 1 considered to be effective in blackening resistance are below 20 k CPS. The situation of hot-dip galvanizing of WL > No treatment It is 3 4 k CPS. ♦ After processing, it is less than 2 kcps. Write this page. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Please read the precautions on the back A before -13. -Milk 600 A7 _B7___ V. Description of the invention (11) Therefore, in order to suppress the blackening phenomenon of the molten zinc-based electroplated steel sheet, it is only necessary to reduce the amount of thickened A 1 on the surface of the electroplating, but it will help Capturing agents for etching phosphate ions and fluoride ions, zinc ions, or aluminum ions in acidic aqueous solution can also be used for sulfuric acid ionization. The content of organic acid ions that also have a pH buffering function, and nickel, cobalt, and iron ions used to replace the function of the plating reaction etching aid, is limited to a specific range, by adjusting the pH to 1.5 to 4.5. , Zinc ions or aluminum ions do not cause a large accumulation, sludge does not occur over a long period of time and can continue to be used, which were discovered by the inventors
Ο I 且，曰本特開平6—293973號公報之下限pH 係由2成爲1 . 5，乃係積極的蝕刻鋁離子之組成之故， 利用連續操作使硫酸鋁離子累積，使pH較向來下限値變 低所致。 經濟部中央櫟準局貝工消费合作社印裝 ^^1 ^^1 I In ^^1 m ^^1 ^^1 '. <請先w讀背面之注意事項再填寫本頁) 又，若使用本發明之方法時，則含有容易變黑的普通 鋅花熔融鍍鋅鋼板亦已'濃化於電鍍最表面之鉛與鋁同樣的 在短時間可減至低濃度爲止，藉由與其後施加的塗布型鉻 酸鹽處理之組合，在不損及美觀的普通鋅花下，可確認出 能提供耐白銹性及耐變黑性優越的熔融鍍鋅鋼板。 如此，本發明之酸性水溶液之作用，由於在熔融鋅系 電鍍鋦板之最表面上已濃化的A 1或P b存在的部位係形 成助長變黑之活性點，故利用去除此等活性點之效果可防 止變黑*又，減少此種活性的部位，且重金屬附著量可予 降低之故，即使進行鉻酸鹽處理，亦被視作可抑制基於局 部電池之腐蝕（白銹發生）之進行。 . 本紙張尺度適用中因8家揲率（CNS M4規格（210X297公釐） • 14- 412$〇〇 A7 _B7___ 五、發明説明（12 ) 實施例 以實施例更詳細說明本發明，且於此等實施例內係供 說明本發明而記載者，並非對本發明有任何限定者。 實施例1〜3及比較例1〜4 於實施例1〜3及比較例1〜4之各個例子，採用表 1所示的組成之處理液連續加工處理下述（1 )記載的供 試試驗板。表中之上段表示連續加工處理前，下段表示連 續加工處理後之硫酸離子、鋅離子、鋁離子量。 其次對處理後之試驗板及未施加處理之供試試驗板（ 比較例4)，施以下述（2)之塗布型鉻酸鹽處理》 因此，對已施以此等處理之各供試試驗板，進行下述 (3)、 （4)之耐變黑促進試驗，及耐白銹促進試驗。 經濟部中央標準局員工消费合作社印装 (請先聞讀背面之注意事項再樓寫本頁) 表2上示出已適用的酸性處理液條件，污泥發生之有無， 處理後的重金屬析出量，表示電鍍表層之A 1去除程度的 利用螢光X射線分析裝置之鋁強度’及耐變黑促進試驗與 耐白錯促進試驗之結果。 表1所示的處理液組成係除有機酸，F e係以 FeS〇4· 7H2〇 ，Co 以 CoS〇4· 7H2O ’Ni 以Ni S〇4 _ 6H2〇，P〇4 以 75% 原磷酸，F 以 40%矽氟化氫酸，Zn以ZnS〇4· 7H2〇，A1以 硫酸礬土（Al2 (S〇4) 3· nH2〇)爲供給源’處理 液p Η係以硫酸及氨予以調整。 本紙張尺度通用中國國家揉準（CNS ) Λ4規格（2丨0X297公釐） -15- Α7 Α7 Β7 五、發明説明（13 > 經濟部中央橾準局貝工消费合作社印装 〔表1〕 \項目 實施\ 例No\ 連續尤 旺時之處理液成分量(g/之） pH Fe Co Ni P〇4 F 有機酸 S0< Zn A1 1 1.5 2.5 0.5 抗壞血酸 5.0 39 25 0 3.1 實 88 53 1.5 2.8 施 2 0.1 冊 1.0 2.0 羥基乙酸 3.5 27 0 5.0 4.2 例 72 27 5.8 3.9 3 2.0 1.0 0.7 1.5 檸檬酸 2.0 18 5 1.0 2.2 61 31 1.9 2.0 1 1.5 m 2.5 0.5 抗壞血酸 5.0 2 0 0 3.2 47 25 1.3 3.0 比 2 • 1.0 2.0 檸檬酸 3.5 0 0 0 3.9 較 6 3 0.2 1.9 例 3 2.0 . 1.0 . 檸檬酸 2.0 18 5 1.0 4.2 40 21 0.8 5.3 40 21 0.8 4.0 4 無^®理 註：僅比較例Νο.3，上段表示連續加工前，中段表示加工後pH未調整•下段表示 加工後pH調整後。 本纸張尺度44用中國國家標率（CNS > A4规格（210X297公釐） ^^^^1 ^^^^1 ^^^^1 J— tttf c^tf 一 ' * , (請先閲讀背面之注意事項再填寫本頁) -16- 41260ο Α7 Β7_ 五、發明説明（14 ) (1) 供試試驗板 (請先閩讀背面之注意事項再填寫本頁) 熔融鍍鋅鋼板（A1 : 0 . 2%，Pb : 0 . 15% ，鍍著量90g/iri，著通鋅花材，板厚0·8mm)無 塗油板 (2) 塗布型鉻酸鹽處理 利用輥塗法將塗布型鉻酸鹽液（含有C r s + — 4% ’ C r3 + — 1%之水溶液）塗布成鉻附著量成2 5mg/iri 後，在2 0 0°C之熱風乾燥爐以最高到達板溫8 0°C予以 乾燥。 (3) 耐變黑促進試驗 由各供試試驗板裁切多片7 Ο X 1 5 Omm之試驗板 ，使各試驗板之試驗面相對面並使疊合成1對者’以聚氯 乙烯被覆紙捆包後，將四角以螺栓鎖緊後，用扭力扳手施 加70kg f · cm之負載，因此，在50 98%相 對濕度之濕潤試驗器內保持240小時後，取出，以下述 判定基準目視判定疊合部之變黑狀況。 經濟部中夹揉準局負工消费合作社印装 ◎:未變黑 〇：極輕度灰色化 △:約略發生灰黑色之變色 X:顯著灰黑色〜色黑色化 (4) 耐白銹促進試驗 由各供試試驗板裁切7〇xl50mm之試驗板，實 施J IS_Z_237 1規定的鹽水噴霧試驗，依下述判 定基準目視判定9 6小時後之白銹發生面積。 本紙張尺度埴用中國國家梯準（CNS )人4規潘（210X297公羞） -17- 412600 A7 B7 五、發明説明（15 ) ◎:無白銹 〇：白銹發生面積率未滿5% △:白銹發生面積率5%〜未滿2 5% X :白銹發生面積率2 5%以上 (請先W讀背面之注意事項再填寫本頁) 經濟部中央揉隼局貝工消费合作社印装 本紙張尺度填用中國困家揉準（CNS ) A4規格（210X297公釐} -18 - 經濟部中央梯準局員工消费合作杜印裝 412600 at B7 五、發明説明（16 ) 〔表2〕 \ ms 處理液 中的污 泥發生 之有被 |J J 1 k\ 處理條件 重金屬析出量 (mg/m) 鋁 強度 (kcps) 耐變黑 促進試 驗結果 耐白銹 促進試 驗結果 實拥 例 \ 處理 方法 CC) 時間 (秒） Fe Co Ni 實 施 例 1 並 噴霧 50 5 2.4 1.3 ◎ ◎ ίΒΕ >»·»> • 2.0 1.3 ◎ ◎ 2 λΤΤΤ ΓΤΤΠ: ^ts\ 浸潰 60 10 0.2 1.5 ◎ ◎ Art /!V\ 0 ' 1.9 〇 ◎ 3 ΑτΤ nir 噴霧 50 3 2.4 0.9 1.4 ◎ 〇 ίκ 1.7 0.6 1.4. ◎ ◎ 比 較 例 1 Μ 〆t、Ί 噴霧 50 5 8.4 1.0 ◎ X /ττΤ Ttnr i\ 1.2 1.5 ◎ ◎ 2 An* «« 浸漬 60 10 3.0 X ◎ 4nL 無 . . 2.8 X ◎ 3 jhre ΤΤΤΓ * i\\ 噴霧 50 3 1.3 0.2 1.8 〇 ◎ 有 0.1 0,1 2.7 X 〇 斑 〆m 0.8 0.2 2.3 Δ 〇 4 _ 3.3 X ◎〇 I. The lower limit pH of Japanese Patent Application Laid-Open No. 6-293973 is 2 to 1.5, which is the composition of active etching of aluminum ions. The continuous operation is used to accumulate aluminum sulfate ions to make the pH lower than the conventional lower limit.値 becomes low. Printed by the Central Oaks Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives ^^ 1 ^^ 1 I In ^^ 1 m ^^ 1 ^^ 1 '. ≪ Please read the notes on the back before filling this page) Also, if When the method of the present invention is used, the ordinary zinc-plated hot-dip galvanized steel sheet containing easy to turn black has been 'concentrated' on the outermost surface of the plating, and the lead can be reduced to a low concentration in a short period of time, like aluminum, by applying it later The combination of the coating type chromate treatment can confirm that it can provide a hot-dip galvanized steel sheet with excellent white rust resistance and blackening resistance without sacrificing the appearance of ordinary zinc. In this way, the effect of the acidic aqueous solution of the present invention is to form active spots that promote blackening at the sites where the concentrated A 1 or P b exists on the outermost surface of the molten zinc-based electroplated slab, so these active spots are removed by using The effect can prevent blackening *, reduce such active sites, and reduce the amount of heavy metal adhesion. Even if chromate treatment is performed, it is considered to inhibit local battery corrosion (white rust). get on. . This paper is applicable for 8 companies (CNS M4 specification (210X297 mm) • 14- 412 $ 〇〇A7 _B7___ V. Description of the invention (12) Examples The invention will be described in more detail with examples, and here The examples are described for the purpose of describing the present invention, and are not intended to limit the present invention in any way. Examples 1 to 3 and Comparative Examples 1 to 4 For each of Examples 1 to 3 and Comparative Examples 1 to 4, tables are used. The treatment liquid of the composition shown in 1 is continuously processed to test the test plate described in (1) below. The upper stage in the table indicates the amount of sulfate ion, zinc ion, and aluminum ion before the continuous processing process and the lower stage. Next, the treated test plate and the untested test plate (Comparative Example 4) were subjected to the following coating type chromate treatment (2). Therefore, each of the test tests to which this treatment has been applied is applied. Plate, carry out the following blackening resistance promotion tests (3) and (4) and white rust resistance promotion test. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before writing this page) ) Table 2 shows the applicable acid treatment liquid strips The presence or absence of sludge, the amount of heavy metal precipitation after the treatment, indicates the degree of A 1 removal of the electroplated surface layer, the strength of aluminum using a fluorescent X-ray analysis device, and the results of the blackening resistance promotion test and the white fault resistance promotion test. The composition of the treatment solution shown in Figure 1 is based on the removal of organic acids, Fe is FeS04 · 7H2O, Co is CoS04 · 7H2O'Ni is NiS04-6H2O, and P04 is 75% orthophosphoric acid. F was adjusted with 40% silicon hydrofluoric acid, Zn with ZnSO4 · 7H2O, and A1 with alumina sulfate (Al2 (SO4) 3 · nH2O) as the supply source. The treatment solution pΗ was adjusted with sulfuric acid and ammonia. The size of this paper is generally in accordance with the Chinese National Standard (CNS) Λ4 specification (2 丨 0X297 mm) -15- Α7 Α7 Β7 V. Description of the invention (13 > \ Project implementation \ Example No \ The amount of the treatment liquid in continuous Uwang (g / of) pH Fe Co Ni P〇4 F organic acid S0 < Zn A1 1 1.5 2.5 0.5 ascorbic acid 5.0 39 25 0 3.1 solid 88 53 1.5 2.8 Application 2 0.1 volume 1.0 2.0 glycolic acid 3.5 27 0 5.0 4.2 cases 72 27 5.8 3.9 3 2.0 1.0 0.7 1.5 citric acid 2.0 18 5 1.0 2.2 61 31 1.9 2.0 1 1.5 m 2.5 0.5 ascorbic acid 5.0 2 0 0 3.2 47 25 1.3 3.0 ratio 2 • 1.0 2.0 citric acid 3.5 0 0 0 3.9 compared to 6 3 0.2 1.9 Example 3 2.0. 1.0. Citric acid 2.0 18 5 1.0 4.2 40 21 0.8 5.3 40 21 0.8 4.0 4 None ^ Note: Only Comparative Example No. 3, the upper section indicates before continuous processing, the middle section indicates that the pH is not adjusted after processing, and the lower section indicates that the pH is adjusted after processing. . This paper size 44 uses the Chinese national standard (CNS > A4 size (210X297 mm) ^^^^ 1 ^^^^ 1 ^^^^ 1 J— tttf c ^ tf a '*, (Please read first Note on the back page, please fill in this page) -16- 41260ο Α7 Β7_ V. Description of the invention (14) (1) Test board (Please read the notes on the back page before filling out this page) Fused galvanized steel sheet (A1: 0.2%, Pb: 0.15%, plating amount 90g / iri, pass through zinc flower material, plate thickness 0 · 8mm) oil-free plate (2) coating type chromate treatment coating by roller coating method Type chromate solution (containing C rs + — 4% 'C r3 + — 1% aqueous solution) is applied to form chromium with an adhesion amount of 25 mg / iri, and then reaches the board temperature in a hot air drying furnace at 200 ° C. Dry at 80 ° C. (3) Blackening resistance promotion test Cut multiple test plates of 7 0 X 1 5 Omm from each test plate, make the test surface of each test plate face to face and superimpose one pair. 'After wrapping with PVC-coated paper, tighten the four corners with bolts, and apply a load of 70 kg f · cm with a torque wrench. Therefore, after keeping it in a humidity tester of 50 98% relative humidity for 240 hours, remove it. Take the following Determine the blackening condition of the superimposed section visually with a reference standard. Printed by the Ministry of Economic Affairs of the Bureau of Work and Consumer Cooperatives ◎: Not blackened 0: Very slight graying △: Grayish blackish discoloration X: Significant grayish black ~ Blackening of color (4) White rust resistance promotion test Cut a test plate of 70x50mm from each test plate, implement the salt spray test specified in J IS_Z_237 1, and visually judge the whiteness after 96 hours according to the following criteria. Occurrence area of rust. This paper uses the standard of China National Standards (CNS) 4 gauge pan (210X297). -17- 412600 A7 B7 V. Description of the invention (15) ◎: No white rust 〇: White rust occurrence area ratio Less than 5% △: The area ratio of white rust occurrence is 5% to less than 2 5% X: The area ratio of white rust occurrence is more than 2 5% (please read the precautions on the back before filling this page) The paper size of the printed copy of the Beige Consumer Cooperative Co., Ltd. is filled with the Chinese Standard for Household Standards (CNS) A4 (210X297 mm) -18-The consumer cooperation of the Central Ladder Bureau of the Ministry of Economy Du printed 412600 at B7 V. Description of the invention (16 ) [Table 2] \ ms Treatment of sludge in the treatment solution occurs | JJ 1 k \ treatment Condition Heavy metal precipitation (mg / m) Aluminium strength (kcps) Blackening resistance promotion test result White rust resistance promotion test result Actual example \ Treatment method CC) Time (seconds) Fe Co Ni Example 1 and spray 50 5 2.4 1.3 ◎ ◎ ίΒΕ > »·» > • 2.0 1.3 ◎ ◎ 2 λΤΤΤ ΓΤΤΠ: ^ ts \ impregnated 60 10 0.2 1.5 ◎ ◎ Art /! V \ 0 '1.9 〇 ◎ 3 ΑτΤ nir spray 50 3 2.4 0.9 1.4 ◎ 〇ίκ 1.7 0.6 1.4. ◎ ◎ Comparative Example 1 Μ 〆t, Ί Spray 50 5 8.4 1.0 ◎ X / ττΤ Ttnr i \ 1.2 1.5 ◎ ◎ 2 An * «« Impregnation 60 10 3.0 X ◎ 4nL None ... 2.8 X ◎ 3 jhre ΤΤΤΓ * i \\ Spray 50 3 1.3 0.2 1.8 〇 ◎ There is 0.1 0,1 2.7 X 〇Pin m 0.8 0.2 2.3 Δ 〇 4 _ 3.3 X ◎
Jn- m^— .1 nn ^n - I (请先M讀背面之注意事項再填寫本頁) 本紙張尺度埴用中國國家揉準（CNS ) A4洗格{ 210X297公釐） -19- 經濟部中央橾率局貝工消費合作社印裝 ^t26〇〇 A7 _B7_五、發明説明（17 ) 由實施例1〜3及比較例1〜4，表1及表2可知有 下述結論。 ① 於實施例1〜3，重金屬析出量可予抑制，耐變黑 性及耐白銹性優越*即使溶出離子量增加亦不發生污泥， 且經長期間可保持其初期性能。 ② 於事先不含有鋅離子或鋁離子之比較例1 ，初期重 金屬析出量變成過量使耐白銹性低劣》 ③ 於不含有重金屬離子之比較例2，在取代電鍍初期 反應之蝕刻反應在短期間內幾乎不引起，耐變黑性低劣》 ④ 在不含有磷酸及氟之比較例3，連續加工處理前由 於某種程度之蝕刻效果，耐變黑性係良好的，惟在連續處 理後之pH調整前，由於pH上升，會發生污泥，同時耐 變黑性低劣，pH調整後亦因蝕刻不足使耐變黑性未能改 善。 ⑤ 於未進行酸性處迪之比較例4，耐變黑性低劣。 實施例4〜6及比較例5〜8 於實施例4〜6及比較例5〜8之各個例子，採用表 3所示的組成之處理液（與表1同法調整）處理於下述（ 1 )記載的供試試驗板上。表中之上段表示連續加工處理 前，下段表示連續加工處理後之硫酸離子、鋅離子，鋁離 子量。其次於處理後之試驗板及未施予處理之供試試驗板 (比較例4 )上，施以下述（2 )之塗布型鉻酸鹽處理。 因此，對施以此等處理之各供試試.驗板，進行下述（ ΙΊ.--K-----策---- {請先wtl背面之注f項再填寫本頁) 本紙張尺度逍用中國國家揉率（CNS ) A4规格（210X297公釐） -20- 412600 A7 B7_ 五、發明説明（18 ) 3)、 （4)之耐變黑促進試驗及耐白銹促進試驗。表4 上示出已適用的酸性處理液條件，連續加工處理供試試驗 板後之有無發生污泥，處理後之重金屬析出量，表示電鍍 表層之A 1去除程度之利用螢光X射線分析裝置的鋁強度 及耐變黑促進試驗與耐白銹促進試驗之結果。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局貝工消费合作杜印製 本紙張尺度適用中國困家標率（CNS ) A4洗格（210X 297公嫠） -21 - A7 B7 五、發明説明（19 ) 經濟部中央搮準局員工消费合作社印製 〔表3〕 \項目 實施\ 例No\ 處理腿成 連續加工 時之處理液成分量（g/1) pH Fe Co Ni P〇4 F 有機酸 S〇4 Zn A] 實 施 例 4 0.5 0.5 1.0 2.0 乳酸 1.2 19 0 3.0 4.0 85 25 8.0 3.5 5 1.0 - - 2.5 1.0 酒石酸 3.0 10 5 0 2.5 67 28 4.2 2.2 6 - 4.5 1.5 2.5 蘋果酸 9.0 64 2 10.0 2.S 130 30 14.5 2.1 比 較 例 5 1.0 - 2.5 - - 10 5 0 2.5 69 39 1.3 1.0 6 - - 10.0 1.5 2.5 蘋果酸 9.0 73 2 10.0 2.0 204 53 19.8 1.5 7 NaOH:20 g/I 硝酸鐵：以Fe計3 g/1 NaAh :以 A1 計 10 g/1 EDTA 2Na 15.0 0 10.0 12.8 - 2 6.1 12.0 8 無酸隨理 (請先聞讀背面之注意事項再填寫本頁) 1訂 本紙張尺度、遑用中國國家揲準（CNS ) A4規格{210X297公釐） -22- 經濟部中央橾窣局負工消费合作杜印製 4^2600 A7 ______B7__ 五、發明説明（20 ) (1 )供試試驗板 熔融鋅一 5%鋁電鍍鋼板（鍍著量9 0 g/nf，板厚 0.5mm)無塗油板 (2 )塗布型鉻酸鹽處理 利用輥塗法將塗布型鉻酸鹽液（含有C r 5 + — 2%， C r 3 + — 1%，膠態二氧化矽5%之水溶液）塗布成鉻附 著量3 Omg/rri後，在2 0 0 °C之熱風乾燥爐內於最高 到達板溫1 0 0 °c予以乾燥。 (3 )耐變黑促進試驗 由各供試試驗板裁切多片7 0 X 1 5 0mm之試驗板 ，使各試驗板之試驗面相對面並使叠合成1對者，以聚氯 乙烯被覆紙捆包後，將四角以螺栓鎖緊後，用扭力扳手施 加70kgf . cm之負載，因此，在50t、98%相 對濕度之濕潤試驗器內保持2 4 0小時後，取出，以下述 判定基準目視判定叠合部之變黑狀況。 ◎:未變黑 〇：極輕度的黑色化 △:約略發生灰黑色之變色 X:顯著的灰黑色〜黑色化 (4 )耐白銹促進試驗 由各供試試驗板裁切7〇x 1 5 0mm之試驗板，實 施J IS — Z — 2371規定的鹽水噴霧試驗，依下述判 定基準目視判定9 6小時後之白銹發生面積。 ◎:無白銹 本纸張尺皮逋用中國國家標準（CNS M4规格（210X297公釐） --1---------装------—訂 -------乳 - (請先閲讀背面之注意事項*»填寫本頁) -23- 412600 A7 B7 五、發明説明（21 ) 〇：白銹發生面積率未滿5% △:白銹發生面積率5%〜未滿2 5% X :白銹發生面積率2 5%以上 ---^---l·-----装------一訂 (請先閣讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印装 本纸張尺虞速用中國®家標準（CNS ) A4%格（210X297公釐） -24- 412600 A7 B7 五 '發明説明（22 ) 經濟部中央橾準局貝工消费合作社印製 〔表4〕 \項目 處理液 中的污 泥發生 之有無 處理條件 重金屬析出量 (mg/rrf) 鋁 強度 (kcps) 耐變黑 mm 驗結果 耐白綉 促進試 驗結果 實S0 例 No\ 處理 方法 溫度 CC) 時間 (秒） Fe Co Ni 實 施 例 4 Μ >Ίν» 噴霧 50 3 0.5 0.2 17.0 ◎ ◎ 無 0.3 0.1 . 18.1 ◎ ◎ 5 噴霧 60 5 2.1 . . 15.5 ◎ ◎ Μ 1.9 . 17.6 ◎ ◎ 6 無 噴霧 50 5 3.1 17.8 ◎ ◎ Μ _ 1.8 18.9 ◎ ◎ 比 較 例 5 無 噴霧 60 5 4.5 . 16.5 ◎ 〇 Μ. J 1 0.4 . • 20.8 Δ ◎ 6 te 噴霧 50 5 . 7.5 12.5 ◎ X Μ i 1 \\ 0.4 19.8 〇 Δ 7 Μ /»1\ 噴霧 50 3 2.5 . 12.5 ◎ ◎ 有 0-1 26.1 Δ ◎ 8 • • 33.8 X ◎ (請先Μ讀背面之注意事項再填寫本頁) *衣. I訂 本紙張尺成逍用中國國家標率（CNS > Α4规格（210Χ297公釐） -25- 經濟部中央揉牟局男工消费合作社印裝 412600 A7 _B7_ 五、發明説明（23 ) 由實施例4〜6 ·比較例5〜8，表3及表4可知有 下述結論。 ① 於實施例4〜6 ，重金屬析出量可予抑制，耐變黑 性及耐白銹性優越，即使溶出離子量增加亦不發生污泥， 且經長期間可保持其初期性能。 ② 於不含有氟離子及有機酸之比較例5，利用連續處 理由於不包含有機酸，pH緩衝能力低且硫酸補給量變多 ，p Η過於降低，會出現裝置腐蝕之危險性，故將處理予 以中斷•且，即使於中斷前不論pH是否較低，由於不含 有氟離子·會由於蝕刻不足使耐變黑性劣化。 ③ 於重金屬離子量較多的比較例6，在初期未能控制 重金屬離子析出量，耐白銹性會低劣*利用其後的連續處 理由於蝕刻量較多，於捕捉鋅或鋁離子所需的硫酸離子量 變成過多，硫酸離子會殘留於試驗板表面上，使耐白銹性 低劣。 ^ ④ 於鹼性鹼之比較例7，由於連續處理會大量發生污 泥，重金屬離子亦共沈澱，故蝕刻不足，而使耐變黑性降 低。 ⑤ 於未予酸性處理的比較例8，耐變黑性會低劣。 發明之功效 於熔融鋅系電鍍鋼板之表面上事先以與本發明有關的 酸性水溶液處理後，藉由施以塗布型鉻酸鹽處理*使耐變 黑性，耐白銹性提高，且經長期間可保.持酸性水溶液之初 本紙張尺矣逍用中Η國家輮準（CNS )戍4規<格（210x297公着) " -26- ---^---η-----^------ir------1 ·* (請先Μ讀背面之注意事碩#填寫本頁) 412600 A7 B7 五、發明説明（24 ) 其 故 形 情 之 置 裝 餓 腐 無 乎 幾 者 再。 ’大 用甚 使値 續價 連用 可利 並的 能上 性業 期工 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央樣準扃負工消费合作社印製 本紙張尺久逍用中國國家標準（CNS ) A4规格（210X297公釐） -27-Jn- m ^ — .1 nn ^ n-I (please read the precautions on the back before filling this page) This paper size is based on China National Standards (CNS) A4 washing grid {210X297 mm) -19- Economy Printed by the Central Government Bureau of Shellfish Consumer Cooperatives ^ t26〇〇A7 _B7_ V. Description of the Invention (17) From Examples 1 to 3 and Comparative Examples 1 to 4, Tables 1 and 2 show the following conclusions. ① In Examples 1 to 3, the amount of heavy metal precipitation can be suppressed, and the blackening resistance and white rust resistance are excellent. Even if the amount of dissolved ions increases, no sludge occurs, and its initial performance can be maintained over a long period of time. ② In Comparative Example 1 which did not contain zinc ions or aluminum ions beforehand, the amount of heavy metals deposited in the initial period became excessive and deteriorated white rust resistance. ③ In Comparative Example 2 which did not contain heavy metal ions, the etching reaction was replaced in a short period of time instead of the initial plating reaction. It is hardly caused in the inside and has poor blackening resistance. ④ In Comparative Example 3, which does not contain phosphoric acid and fluorine, the blackening resistance is good due to some degree of etching effect before continuous processing, but the pH after continuous processing Before the adjustment, sludge occurred due to the increase in pH, and the blackening resistance was poor. After the pH adjustment, the blackening resistance could not be improved due to insufficient etching. ⑤ In Comparative Example 4 without acid treatment, the blackening resistance was poor. Examples 4 to 6 and Comparative Examples 5 to 8 Each of Examples 4 to 6 and Comparative Examples 5 to 8 was treated with a treatment liquid having the composition shown in Table 3 (adjusted in the same manner as in Table 1) and processed as follows ( 1) Record the test board. The upper part of the table indicates the amount of sulfate ion, zinc ion, and aluminum ion before the continuous processing. Next, the coated test chromate treatment (2) described below was applied to the treated test plate and the test test plate (Comparative Example 4) to which no treatment was applied. Therefore, for each of these treatments, try the test board and perform the following (ΙΊ .-- K ----- 策 ---- {Please note the f item on the back of wtl before filling out this page) This paper is scaled to the Chinese National Kneading Rate (CNS) A4 specification (210X297 mm) -20- 412600 A7 B7_ V. Description of the invention (18) 3), (4) Blacking resistance promotion test and white rust promotion test . Table 4 shows the applicable conditions of the acidic treatment solution, the presence or absence of sludge after continuous processing of the test test plate, and the amount of heavy metal precipitation after the treatment, which indicates the degree of A 1 removal on the plating surface, using a fluorescent X-ray analysis device The results of aluminum strength and blackening resistance promotion test and white rust resistance promotion test. (Please read the precautions on the back before filling out this page) Printed paper scales of the Central Bureau of Standards and Quarantine, Ministry of Economic Affairs, printed paper are applicable to China's Standards for Standardization (CNS) A4 Washing (210X 297 cm) -21- A7 B7 V. Description of the invention (19) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs [Table 3] \ Project Implementation \ Example No \ The amount of the processing liquid when the legs are processed continuously (g / 1) pH Fe Co Ni P〇4 F organic acid S04 Zn A] Example 4 0.5 0.5 1.0 2.0 Lactic acid 1.2 19 0 3.0 4.0 85 25 8.0 3.5 5 1.0--2.5 1.0 Tartaric acid 3.0 10 5 0 2.5 67 28 4.2 2.2 6-4.5 1.5 2.5 Malic acid 9.0 64 2 10.0 2.S 130 30 14.5 2.1 Comparative example 5 1.0-2.5--10 5 0 2.5 69 39 1.3 1.0 6--10.0 1.5 2.5 Malic acid 9.0 73 2 10.0 2.0 204 53 19.8 1.5 7 NaOH: 20 g / I ferric nitrate: 3 g / 1 Fe 1 NaAh 10 g / 1 A1 EDTA 2Na 15.0 0 10.0 12.8-2 6.1 12.0 8 No acid (please read the precautions on the back before filling in this Page) 1 book size, using China National Standards (CNS) A4 specifications {210X297 mm) -22- Central Ministry of Economic Affairs Printed by the Bureau of Work and Consumption Cooperation Du ^ 2600 A7 ______B7__ V. Description of the invention (20) (1) Test plate molten zinc-5% aluminum electroplated steel plate (plating amount 90 g / nf, plate thickness 0.5mm) ) Oil-free plate (2) Coating type chromate treatment The coating type chromate solution (containing C r 5 + — 2%, C r 3 + — 1%, colloidal silicon dioxide 5% by roller coating method) Aqueous solution) was applied to a chromium adhesion amount of 3 Omg / rri, and then dried in a hot air drying furnace at 200 ° C at a maximum temperature of 100 ° C. (3) Blackening resistance promotion test A plurality of test plates of 70 x 150 mm are cut from each test test plate, so that the test surfaces of the test plates face each other and are superimposed into a pair, and the paper is covered with polyvinyl chloride. After packing, tighten the four corners with bolts, and apply a load of 70 kgf.cm with a torque wrench. Therefore, keep it in a humidity tester of 50t and 98% relative humidity for 24 hours, then take it out, and visually check it according to the following criteria Determine the blackening condition of the overlapped part. ◎: Not darkened 〇: Very slight blackening △: Discoloration of grayish black occurs approximately X: Significant grayish black to blackened (4) White rust resistance promotion test Cut by each test board 70x 1 A 50 mm test plate was subjected to a salt water spray test specified in J IS — Z — 2371, and the white rust occurrence area was visually determined after 96 hours according to the following determination criteria. ◎: Chinese white paper ruler with non-white rust paper (CNS M4 specification (210X297 mm)) --------------------------------- Order --Milk- (Please read the precautions on the back first * »Fill in this page) -23- 412600 A7 B7 V. Description of the invention (21) 〇: The area ratio of white rust is less than 5% △: The area ratio of white rust is 5 % ~ Less than 2 5% X: The area ratio of white rust occurrence is more than 2 5% --- ^ --- l · ----- installation ----- order (please read the precautions on the back first) (Fill in this page again.) Printed paper ruler of the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, China Quick Use China® Standard (CNS) A4% grid (210X297 mm) -24- 412600 A7 B7 Five 'Invention Description (22 ) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs [Table 4] \ Presence or absence of sludge in the treatment solution of the project Heavy metal precipitation (mg / rrf) Aluminum strength (kcps) Resistance to blackening mm Test result resistance White embroidery promotion test results S0 Example No \ Processing method temperature CC) Time (seconds) Fe Co Ni Example 4 Μ > Ίν »Spray 50 3 0.5 0.2 17.0 ◎ ◎ No 0.3 0.1. 18.1 ◎ ◎ 5 Spray 60 5 2.1 ... 15. ◎ Μ 1.9. 17.6 ◎ ◎ 6 No spray 50 5 3.1 17.8 ◎ ◎ Μ _ 1.8 18.9 ◎ ◎ Comparative Example 5 No spray 60 5 4.5. 16.5 ◎ OM. J 1 0.4. • 20.8 Δ ◎ 6 te spray 50 5. 7.5 12.5 ◎ X Μ i 1 \\ 0.4 19.8 〇Δ 7 Μ / »1 \ spray 50 3 2.5. 12.5 ◎ ◎ Yes 0-1 26.1 Δ ◎ 8 • • 33.8 X ◎ (Please read the precautions on the back before filling This page) * Clothes. I paper ruler becomes a Chinese national standard (CNS > Α4 size (210 × 297 mm) -25- Printed by the Male Workers Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs 412600 A7 _B7_ V. Invention Explanation (23) From Examples 4 to 6 · Comparative Examples 5 to 8, Tables 3 and 4 show the following conclusions. ① In Examples 4 to 6, the amount of heavy metal precipitation can be suppressed, and the resistance to blackening and whitening can be suppressed. Excellent rust, no sludge even if the amount of dissolved ions is increased, and its initial performance can be maintained for a long time. ② In Comparative Example 5 which does not contain fluoride ions and organic acids, since continuous processing does not include organic acids, the pH buffering capacity is low and the amount of sulfuric acid replenishment is increased, and p Η is too low, which may cause the risk of corrosion of the device. Interruption • Even if the pH is not low before interruption, since it does not contain fluoride ions, the blackening resistance is deteriorated due to insufficient etching. ③ In Comparative Example 6, which has a large amount of heavy metal ions, the amount of heavy metal ions precipitated cannot be controlled at the initial stage, and the white rust resistance will be inferior. * The subsequent continuous processing has a large amount of etching, which is necessary for capturing zinc or aluminum ions. The amount of sulfuric acid ions becomes excessive, and sulfuric acid ions will remain on the surface of the test board, making the white rust resistance inferior. ^ ④ In Comparative Example 7 of alkaline alkali, due to continuous treatment, a large amount of sludge occurred, and heavy metal ions also co-precipitated, so the etching was insufficient and the blackening resistance was reduced. ⑤ In Comparative Example 8 which was not subjected to an acid treatment, the blackening resistance was inferior. Efficacy of the invention After the surface of the molten zinc-based electroplated steel sheet is treated with an acidic aqueous solution related to the present invention in advance, the coating-type chromate treatment is applied * to improve the blackening resistance, white rust resistance, and longevity. Guaranteed during the period. The original paper with an acidic aqueous solution is not used in the Chinese National Standards (CNS) Standard 4 < Grid (210x297) " -26- --- ^ --- η --- -^ ------ ir ------ 1 · * (please read the note on the back first # fill in this page) 412600 A7 B7 V. Description of the invention (24) Pretend to be hungry and few more. 'Great use even makes the renewal price can be used in conjunction with the profitable sex industry (please read the precautions on the back before filling out this page) Central Ministry of Economics Prospective Consumers Cooperatives Print this paper ruler Jiuxiao With China National Standard (CNS) A4 specification (210X297 mm) -27-