201042082 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製造在鋅、鋁或鎂亦及該等金屬之合 金表面上基本上不含鉻（VI)之腐蝕保護層之方法。 【先前技術】 種以轉換層使陰極腐餘保護系統之保護作用增加及作 為清漆及油漆底漆之用途已為吾人知曉許久。除了磷化處 Ο201042082 VI. Description of the Invention: [Technical Field] The present invention relates to a method of producing a corrosion-protective layer substantially free of chromium (VI) on the surface of zinc, aluminum or magnesium and the alloy of such metals. [Prior Art] It has been known for a long time that the conversion layer enhances the protection of the cathode corrosion protection system and serves as a varnish and paint primer. In addition to phosphating
理法之外，已確立一種使表面進行鉻酸鹽處理之方法，尤 其針對含辞基材、含鋁基材及含鎂基材而言。 此Ν況下待處理之表面曝露於其主成分為鉻（VI)化合 物之處理/谷液由此製得之轉換層因此亦包括鉻（VI)離 子。鉻酸鹽處理層大體上顯示良好腐餘保護及良好裝飾之 性質。使用含路（VI)溶液或含鉻（VI)塗層之優點為鉻㈤ 化合物之毒理學性質。因此，例如，含鉻(VI)轉換層之用 途會極大地受限於EC指令2000/53/EC(EC舊車指令㈣ vehicle directVIe))。 已提議，作祕酸鹽處理溶液之替代品，對照絡酸鹽處 理而言，含鉻（III)之酸處理溶液通稱為「純化物」或「純 化溶液r例如’如DE 196 15 664 A1中所提議般 處理溶液基本上係藉由礦物酸溶液中之鉻(111)鹽/ 或經錢酸、及㈣組成。在約4G至6Gt之高溫下^ 等稱為「厚膜鈍化」之方法，以得到足以使鋅表= 免遭腐蝕之鈍化層厚度。兩力古认― 又饰瘦 旱度而在两於室溫之溫度下進行兮古 法係由於鉻（ΠΙ)離子相對於鉻㈣離子之反應性特m 147617.doc 201042082 不足所致。作為溫度增加之替代之反應時間之明顯增加一 般由於經濟原因而不可行。 作為替代方法’可藉著利用如US 5,41 5，702中所述額外 包括磷之含氧酸之酸性含鉻（ΙΠ)溶液處理，而在辞_鎳合金 層上製得不含Cr(VI)之黑色轉換層。在該方法中，形成具 有良好裝飾性質之均勻黑色轉換層。 WO 03/05429描述同樣採用額外包括磷酸根離子之含鉻 (ΙΠ)酸性處理溶液製得之類似之轉換層。此同樣具有良好 裝飾性質而沒有進一步進行後處理步驟（諸如密封）之表面 無法達成令人滿意之腐韻保護性質。 EP 1 484 432 A1描述用於鋅合金表面之包括鉻（ΙΠ)離子 及硝酸根亦及羧酸（諸如酒石酸、馬來酸、草酸、琥珀 酸、檸檬酸、丙二酸或己二酸）之含絡⑽黑色純化溶^。 為改良腐㈣護，㈣該等溶液處理之表面必須經過隨後 之密封。該等處理溶液係在高於正f室溫之溫度下採用。 US 2004/0 i 5 6999同樣描述一種用⑨使辞合金表面進行 黑色鈍化之方法。該等處理溶液包括絡（ιπ)離子及含碟陰 離子亦及械根及有顧酸。所給有機羧酸之實例為料 酸、酒石酸、馬來酸' 甘油酸、乳酸、乙醇酸、丙二酸、 破ίό酸、草酸及戊二酸。 基本上’在製造保護層中進行以下製程步驟：使金屬表 面活化，在酸性鈍化浴中製得轉換層，藉由—次或更多次 清洗操作使侵㈣鈍化浴液自該表面移除，進行乾燥繼而 施用另-種密封劑或在後浸塗溶液中進行後浸塗繼而進行 147617.doc 201042082 乾燥。 1亥過程具有如下缺點：ί青洗廢水被相當大量4金屬污染 且形成可能之錯合劑之，並必須加以處置或以複雜且昂責 . 之方式進行處理。 -- 由於該等缺點’近來，吾人已努力發展「免清洗」法。 隋况下基本上施加包括使鈍化增加之金屬組分（例如 鉻鈦或I )、亦及藉由有機聚合物組成之膜成形組分之 ❹轉換層1¾等方法主要用於紹表面之處理。亦通常描述與 媒成形聚合物組合之「免清洗」填化處理。 因此例如文獻US 6，117,251描述可使金屬表面進行磷 酸鋅處理之包括氧化鋅、鱗酸、聚乙稀醇及另一種金屬鹽 之水性溶液。 "°" 就鋅、纟S及鎮表面而言，料方法之使用僅僅係極其有 限因為儘g其可形成後入有機基質中之膜但是令人滿 〜之腐蚀保所而要之封閉氧化鉻層或表面金屬混合氧化 ❹ 物層並未形成。 【發明内容】 本發月之冑目標係提供一種用於使辞、銘或鎂亦及該 等金屬合金之金屬表面進行不含鉻（VI)鈍化之方法，藉由 肖方法’該等表面可得到極其良好之腐㈣護性質，而同 ， 時不會獲得經污染之清洗水。 【實施方式】 該目標可藉由-種在鋅、紹或鎂表面亦及該等金屬合金 表面形成腐#保護層之方法實現，該方法包括如下步驟： 147617.doc 201042082 i) 使前述金屬或所提及之金屬合金表面與包括如下之溶 液接觸： 鉻（III)離子， 選自前述之表面金屬鋅、鋁或鎂或表面金屬合金之金 屬離子， 及至少一種選自由羧酸、聚羧酸、羥基叛酸、胺基羧 酸、醇' 胺基趟組成之群之錯合劑， 其中該處理溶液具有1.0至4.0之pH。 ii) 然後，使所提及之等金屬之表面與包括如下之溶液直 接接觸， 鉻（III)離子， 選自前述之表面金屬辞、鋁或鎂或表面金屬合金之金 屬離子， 及至少一種選自由羧酸、聚羧酸、羥基羧酸、胺基羧 酸、醇、胺及醚組成之群之錯合劑， 其中該處理溶液具有3.〇至12.0之pH。 在所提及之金屬及金屬合金表面形成腐蝕保護層之方法 ’金屬表面經過鈍化In addition to the chemistry, a method of subjecting the surface to chromate treatment has been established, particularly for conjugated substrates, aluminum-containing substrates, and magnesium-containing substrates. In this case, the surface to be treated is exposed to a treatment/valley solution whose main component is a chromium (VI) compound, and thus the conversion layer thus produced also includes chromium (VI) ions. The chromate treatment layer generally exhibits good corrosion protection and good decorative properties. The advantage of using a path containing (VI) solution or a chromium (VI) containing coating is the toxicological properties of the chromium (f) compound. Thus, for example, the use of a chromium (VI) containing conversion layer is greatly limited by the EC Directive 2000/53/EC (EC vehicle direct VIE). It has been proposed to use a chromium (III)-containing acid treatment solution as a substitute for the acid salt treatment solution, which is generally referred to as "purified material" or "purified solution r such as in DE 196 15 664 A1. The proposed treatment solution consists essentially of chromium (111) salt in the mineral acid solution / or by acid acid, and (iv). At a high temperature of about 4G to 6Gt, etc., it is called "thick film passivation". To obtain a passivation layer thickness sufficient to make the zinc table = corrosion free. Two forces have been recognized - and they are thin and dry. The temperature is measured at two temperatures at room temperature. The reaction of chromium (ΠΙ) ions with respect to chromium (tetra) ions is caused by the lack of m 147617.doc 201042082. The significant increase in reaction time as an alternative to temperature increase is generally not feasible due to economic reasons. As an alternative, it can be prepared by using an acidic chromium-containing solution containing phosphorus oxyacid as described in US Pat. No. 5,41 5,702, and without Cr (VI) on the nickel-alloy layer. ) The black conversion layer. In this method, a uniform black conversion layer having good decorative properties is formed. WO 03/05429 describes a similar conversion layer which is also prepared using a chromium (ΙΠ) acidic treatment solution additionally comprising phosphate ions. This surface, which also has good decorative properties without further post-treatment steps (such as sealing), does not achieve satisfactory rosy protection properties. EP 1 484 432 A1 describes the use of chromium (ruthenium) ions and nitrates as well as carboxylic acids (such as tartaric acid, maleic acid, oxalic acid, succinic acid, citric acid, malonic acid or adipic acid) for the surface of zinc alloys. Containing the complex (10) black purified solution ^. In order to improve the rot (4) protection, (4) the surfaces treated by the solutions must be subsequently sealed. The treatment solutions are employed at temperatures above normal room temperature. US 2004/0 i 5 6999 also describes a method of black passivation of the surface of an alloy. The treatment solutions include complex (ιπ) ions and disc-containing anions as well as roots and acids. Examples of the organic carboxylic acid to be given are acid, tartaric acid, maleic acid 'glyceric acid, lactic acid, glycolic acid, malonic acid, leucovoric acid, oxalic acid and glutaric acid. Basically 'the following process steps are carried out in the manufacture of the protective layer: the metal surface is activated, the conversion layer is produced in an acid passivation bath, and the invading (iv) passivation bath is removed from the surface by one or more cleaning operations, Drying is followed by application of another sealant or post-dip coating in a post-dip coating followed by 147617.doc 201042082 drying. The 1 hai process has the following disadvantages: The ash washing wastewater is contaminated with a considerable amount of 4 metals and forms a possible miscible agent and must be disposed of or treated in a complicated and rigorous manner. -- Due to these shortcomings, recently, we have worked hard to develop the "no-clean" method. In other cases, a method of substantially applying a metal component (e.g., chromium titanium or I) which increases passivation, and a tantalum conversion layer 126 which is a film forming component composed of an organic polymer is mainly used for the treatment of the surface. A "no-clean" filling process in combination with a media forming polymer is also generally described. Thus, for example, the document US 6,117,251 describes an aqueous solution comprising zinc oxide, scaly acid, polyethylene glycol and another metal salt which allows the metal surface to be treated with zinc phosphate. "°" In the case of zinc, bismuth S and the surface of the town, the use of the material method is only extremely limited because it can form a film that is later incorporated into the organic matrix but is full of corrosion protection. The chromium oxide layer or the surface metal mixed cerium oxide layer is not formed. SUMMARY OF THE INVENTION The object of the present month is to provide a method for the chrome-free (VI) passivation of the metal surface of the metal alloys of the syllabus, the syllabus or the magnesium, and the surface of the metal alloy. Obtaining extremely good rot (four) protection properties, while the same, will not get contaminated cleaning water. [Embodiment] The object can be achieved by a method for forming a rust #protective layer on the surface of zinc, samarium or magnesium and the surface of the metal alloy, the method comprising the following steps: 147617.doc 201042082 i) making the aforementioned metal or The metal alloy surface mentioned is in contact with a solution comprising: chromium (III) ions, metal ions selected from the aforementioned surface metals such as zinc, aluminum or magnesium or surface metal alloys, and at least one selected from the group consisting of carboxylic acids and polycarboxylic acids. A complexing agent of a group consisting of a hydroxyl acid, an aminocarboxylic acid, and an alcohol 'amino hydrazine, wherein the treatment solution has a pH of from 1.0 to 4.0. Ii) then, the surface of the metal referred to is directly contacted with a solution comprising chromium (III) ions selected from the foregoing surface metal, metal ions of aluminum or magnesium or surface metal alloys, and at least one selected A complexing agent of a group consisting of a free carboxylic acid, a polycarboxylic acid, a hydroxycarboxylic acid, an aminocarboxylic acid, an alcohol, an amine, and an ether, wherein the treatment solution has a pH of from 0.3 to 12.0. Method of forming a corrosion protection layer on the surface of metals and metal alloys mentioned ‘The metal surface is passivated
方法中需要之清洗操作會產生污 147617.doc 之特徵在於：在該方法之第—步驟中， 且在第二步驟中，於具有近似該組成 之腐飯保護，可省略。 生污染有重金屬離子及 201042082 其他化學品且必須進行相者 繼而導致環境污染。$費用之處置及純化之廢水， 鳟夫為 <方法使鈍化及後處理兩者首次在表面之腐蝕保 不利之影響下，採用具有基本上相同組分之溶液成 馬可能。 兩步驟中♦液不同阳值之把向設定使本身相同之處理溶 液之功能得到控制。 Ο 使步驟1中所採用之基本上藉由鉻㈣鹽及針對金屬 辞、鎮或紹及其合金而言之錯合劑組成之處理溶液設定至 1.0至4.0之pf^.2至3 〇為較佳j⑴$為最佳。因此，根 據溶液之最初PH’可採用酸或驗。硫酸及硝酸尤其適用於 作為酸。較佳採用驗金屬氫氧化物（具體之仏⑽及刪 作為鹼。 鉻（ΠΙ)離子可以無機鉻（ΠΙ)鹽（諸如鹼式硫酸鉻（in)、氫 氧化鉻（III)、磷酸二氫鉻（111)、氣化鉻（ΠΙ)、硝酸鉻 〇 (ΙΠ)、硫酸鉀鉻（111))或有機酸之鉻（ΙΠ)鹽（例如甲磺酸鉻 (HI)、檸檬酸鉻（III))之形式加至處理步驟丨及2之處理溶 液，或可藉由合適之鉻（VI)化合物在存在合適之還原劑下 進行還原得到。例如，合適之鉻（VI)化合物為氧化鉻 (VI)、鉻酸鹽（諸如鉻酸鉀或鉻酸鈉）、重鉻酸鹽（諸如重鉻 . 酸鉀或重鉻酸鈉）。例如，原位產生鉻（III)離子之合適之還 原劑為亞硫酸鹽（諸如亞硫酸鈉）、二氧化硫、亞磷酸鹽（諸 如次磷酸鈉）、磷酸、過氧化氫 '甲醇、葡萄糖酸。鉻（111) 離子亦可以無機鉻（ΙΠ)鹽、鉻（VI)鹽及合適還原劑之混合 147617.doc 201042082 物之形式進行添加。 兩種處理/合液咸包括含量為0.5至10 g/l之鉻（III)，2至 6g/l為較佳及2·5至3.5g/i為最佳。 步驟1之處理溶液一般具有1〇至4〇芄之溫度，2〇至3〇充 為較佳。 於4處理洛液中之處理時間較佳為1〇至6〇〇 s，更佳為 至120s ’最佳為3〇至9〇 s。 在該方法之一個較佳之實施例中，純化處理在鈍化溶液 中係藉由連接基材作為陰極得到促進。此情況下，該基材 上之陰極電流密度較佳為〇.〇5至10 A/dm2,更佳為 至5 A/dm2，最佳為〇」至3 A/dm2。 吾等假設，在第一步驟中，在所設定之強酸性pH值下， 含鉻（III)物種在處理溶液中明顯優先發生鈍化反應。結 果’在該步驟中，不滲透鈍化層極其可靠地在遍及鋅、鎂 或铭及其合金金屬表面之整個區域上形成。然而，該層還 未具特定之耐用性’具體言之，幾乎無抗機械應力性。 第一步驟中形成之鈍化層因此得到固定及因此在第二步 驟中實現耐用性。 步驟2中之處理溶液同樣係基本上藉由鉻（111)鹽及針對 金屬鋅、鎂或鋁亦及其合金而言之錯合劑組成。將該溶液 設定至2.0至12.0之pH，較佳為3.0至7.0，最佳為3 5至 5.0。因此’根據溶液之最初pH，可採用酸或鹼。硫酸及 硝酸尤其適用於作為酸。較佳採用鹼金屬氫氧化物（具體 之NaOH及KOH)作為鹼。 147617.doc 201042082 步驟2之處理溶液一般具有⑺至川^之溫度，4〇至 為較佳。 於該處理溶液中之處理時間較佳為5至6〇〇3，更佳為名至 120 s，最佳為1〇至9〇 s。 在第二步驟中，處理溶液之鈍化用組分實際上不扮演任 何角色’以致該方法可藉由第二步驟中最初藉由唯一之錯The cleaning operation required in the method produces contamination. 147617.doc is characterized in that, in the first step of the method, and in the second step, the sapostat protection having an approximate composition can be omitted. Raw contamination with heavy metal ions and 201042082 other chemicals and must be carried out in the end lead to environmental pollution. The cost of disposal and purification of wastewater, the coward is < method to make passivation and post-treatment both for the first time under the influence of the corrosion of the surface, the use of a solution with substantially the same composition may become possible. In the two steps, the function of the different positive values of the liquid is set to control the function of the same treatment solution. Ο The treatment solution consisting essentially of the chromium (tetra) salt and the complexing agent for the metal, town, or alloy and the alloy used in the step 1 is set to a pf^.2 to 3 1.0 of 1.0 to 4.0. Jia j(1)$ is the best. Therefore, acid or test can be used depending on the initial pH of the solution. Sulfuric acid and nitric acid are especially suitable as acids. Preferably, the metal hydroxide (specifically, ruthenium (10) and the base are used. The chromium (ΠΙ) ion may be an inorganic chromium (ΠΙ) salt (such as basic chromium sulfate (in), chromium (III) hydroxide, dihydrogen phosphate Chromium (111), vaporized chromium (ruthenium), chrome (〇), potassium sulphate (111) or chromium (ΙΠ) salts of organic acids (such as chromium methane sulfonate (HI), chromium citrate (III) The form of the)) is added to the treatment solution of the treatment steps 2 and 2, or may be obtained by reduction of a suitable chromium (VI) compound in the presence of a suitable reducing agent. For example, a suitable chromium (VI) compound is chromium oxide ( VI), chromate (such as potassium chromate or sodium chromate), dichromate (such as heavy chromium. potassium or sodium dichromate). For example, a suitable reducing agent for in-situ generation of chromium (III) ions It is a sulfite (such as sodium sulfite), sulfur dioxide, phosphite (such as sodium hypophosphite), phosphoric acid, hydrogen peroxide 'methanol, gluconic acid. Chromium (111) ions can also be inorganic chromium (strontium) salts, chromium (VI) A mixture of salt and a suitable reducing agent is added in the form of 147617.doc 201042082. Two treatments/liquid combination Including chromium (III) in an amount of 0.5 to 10 g/l, preferably 2 to 6 g/l and preferably 2.5 to 3.5 g/i. The treatment solution of step 1 generally has 1 to 4 Å. The temperature is preferably from 2 Torr to 3 Torr. The treatment time in the 4 treatment solution is preferably from 1 〇 to 6 〇〇s, more preferably to 120 s 'optimally from 3 〇 to 9 〇 s. In a preferred embodiment of the method, the purification treatment is promoted in the passivation solution by connecting the substrate as a cathode. In this case, the cathode current density on the substrate is preferably 〇.5 to 10 A/dm2. More preferably, it is 5 A/dm2, and the best is 〇" to 3 A/dm2. We assume that in the first step, at the set strong acidic pH value, the chromium (III) species in the treatment solution The passivation reaction is clearly prioritized. Results 'In this step, the impermeable passivation layer is extremely reliably formed over the entire surface of the zinc, magnesium or metal surface of the alloy and its alloy. However, the layer has not yet been specifically durable. 'Specifically, there is almost no resistance to mechanical stress. The passivation layer formed in the first step is thus fixed and thus achieved in the second step The treatment solution in step 2 is also basically composed of a chromium (111) salt and a complexing agent for the metal zinc, magnesium or aluminum and alloys thereof. The solution is set to a pH of 2.0 to 12.0, It is preferably from 3.0 to 7.0, most preferably from 3 5 to 5.0. Therefore, depending on the initial pH of the solution, an acid or a base can be used. Sulfuric acid and nitric acid are particularly suitable as an acid. It is preferred to use an alkali metal hydroxide (specifically, NaOH). And KOH) as a base. 147617.doc 201042082 The treatment solution of step 2 generally has a temperature of (7) to chuan, preferably 4 〇. The treatment time in the treatment solution is preferably from 5 to 6 Torr, more preferably from 120 to s, most preferably from 1 to 9 s. In the second step, the passivating component of the treatment solution does not actually play any role, so that the method can be initially overcome by the single step.
合劑組成之溶液及由於夾帶而唯一在生產製程過程中應用 步驟1及步驟2處理溶液之組成進行修改。 〇等假叹，在第二步驟中，在所設定之較弱酸性、中性 或驗性PH值下，錯合劑在處理溶液中明顯優先發生固定反 應、结果’已先前施用在遍及金屬表面整個區域上之鈍化 層在該7驟中付到可靠固定。僅僅由於該步驟，在該表面 上形成可長期耐受機械及其他應力之耐用性腐蝕保護層。 辞、、鎭或IS或其合金可電化學沈積於基材上或已藉由其 (諸如熱鍍鋅）進行施用，或可組成待處理構件之材 料°亥等方法為熟習此項相關技藝之人士知曉。 般用於含辞表面之不含鉻（VI)之純化溶液大體上包 ^鉻（III)離子之來源及—種或多種錯合齊卜該等溶液為熟 習此項相關技藝之人士知曉。處理溶液之般小於2。 在本發明方法之兩步驟中’錯合劑係選自由如下組成之 群肢聚缓酸、經基缓酸、胺基缓酸、醇、醚及胺。 合適之錯合劑為甲酸、乙酸、丙酸、丁酸、異丁酸、戊 =己料酸、環戊《酸、乙醯基水揚酸、$甲酸、石肖 土本甲酸、3,5-二硝基苯甲酸、四氫呋喃_2_曱酸、山梨 147617.doc 201042082 酸草酉夂、丙二酸、號轴酸、戊二酸、己二酸、庚二酸、 辛二酸、壬二酸、癸二酸、馬來酸、苯二甲酸、對苯二甲 酸、伸乙二氮基四乙酸、乙二胺四乙酸、二伸乙基二胺五 =酸、氮基三乙酸、酒石酸、檸檬酸、異擰檬酸、蘋果 酸、抗壞血酸、乳酸、葡萄糖酸、葡糖醛酸、沒食子酸、 :醇、乙醇、1-丙醇'2-丙醇、1-丁醇、2_ 丁醇、卜戊 醇乙一醇、丙一醇、乙二醇丁醚及乙二醇醚。 兩種處理溶液各者中所有錯合劑之含量各為0.75至200 g/卜較佳為5至1〇〇 g/丨，最佳為1〇至5〇 g/1。 當待處理之表面係由鋅或鋅合金組成時，兩種處理溶液 包括3量各為0.75至200 mmol/1之水溶性鋅化合物，較佳 為3至100軸〇丨/1，最佳為10至40 mmol/卜 當待處理之表面係由鎂或鎂合金組成時，兩種處理溶液 包括含量各為2至210 mmol/1之水溶性鎂化合物，較佳為8 至75 mm〇l/卜最佳為12至40 mmol/卜 當待處理之表面係由鋁或鋁合金組成時，兩種處理溶液 包括含量各為1.8至185 mmol/1之水溶性鋁化合物，較佳為 7.5 至 85 mmol/1’ 最佳為 η 至 40 mmol/1。 處理步驟1及2中之兩浴視需要包括選自由NaF、KF、 NH4F、NaHF2、KHF2及NH4HF2組成之群之氟離子之來 源。氟離子係以各為0.001至10 g/丨之含量添加，較佳為 0.01至5 g/Ι及最佳為0.05至2 g/Ι。 處理步驟1及2中之兩浴視需要包括選自由Naa、KC1及 ΝΗβι組成之群之氣離子之來源。氯離子係以各為〇 〇ι至 147617.doc -10- 201042082 • 20 gA之含量添加，較佳為〇.1至10 g/丨及最佳為〇 5至5 g/1。 • 處理步驟1及2之兩浴中另一種視需要之組分為鱗酸鹽化 合物，且至少一種磷酸鹽化合物係選自由如下組成之群： . 正磷酸、聚磷酸、偏磷酸、此等酸之鹽、具有含至多12個 … 碳原子之有機基之此等酸之酯及該等化合物之混合物。磷 、 酸鹽化合物係以各為〇.5至100 g/Ι之含量添加，較佳為3至 50 g/Ι及最佳為5至20 g/I。 0 為增加腐钮保護’選自由Sc、Y、Ti、Zr、Mo、W、 Μη、Fe、Co、Ni、Zn、B、A卜Si組成之群之至少一種金 屬或類金屬可在處理步驟丨及2中視需要添加至兩種處理溶 液。該#元素可以其鹽<形式或以肖合陰離子或該等陰離 子之相應酸（例如六氟硼酸、六氟矽酸、六氟酞酸或六氟 锆酸、四氟硼酸或六氟磷酸）或其鹽之形式添加。 本發明之方法可用於極多鈍化系統中。當可溶性鈷鹽係 以各為0·2至3 g/1(較佳為g/1)之含量添加至處理步驟 ❹及2中之各個洛時，可實現黑色鈍化之優秀腐蝕保護價 值。 —針對後處理而言，已取自處理溶液2之基材係在沒有進 ―先如之’月洗下進行乾燥。例如’乾燥可在乾燥鼓中完 成點附在乾燥鼓中處理溶液2之殘餘物可藉由熱驗溶液 • 之方式移除。 實例 製得具有以下組成之水性反應溶液： 用於步驟1之反應溶液： 147617.doc 201042082 以74重量。/。強度之硝酸鉻（III)溶液之形式添加之3 61 g/1 之Cr(III)離子、10.9 g/1之磷酸根離子、2 5 g/1之鋅離子、 12.1 g/Ι之葡萄糖酸、1〇 之酒石酸、〇 〇88吕以之氟離子 及1.22 g/Ι之氣離子。 藉由硝酸使該溶液之pH設定至1.8。 用於步驟2之反應溶液： 以74重量％強度之硝酸鉻（111)溶液之形式添加之3 6i g/i 之Cr(III)離子、10.9 g/1之磷酸根離子、25 g/1之鋅離子、 i2.i gn之葡萄糖酸、ίο g/i之酒石酸、〇 〇88笆八之氟離子 及1_22 g/ι之氯離子。 藉由氫氧化鈉使該溶液之pH設定至4。 在酸性辞電解質（商標名：獲自At〇tech DeuW-ndThe composition of the mixture and the composition of the treatment solution in steps 1 and 2 are modified by the entrainment process only during the production process.假 假 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The passivation layer on the area is reliably fixed in the 7 steps. Due to this step, a durable corrosion protection layer which can withstand mechanical and other stress for a long period of time is formed on the surface. Words, sputum or IS or alloys thereof can be electrochemically deposited on a substrate or have been applied by (such as hot-dip galvanizing), or a material that can constitute a member to be treated, etc. People know. Purified solutions containing chromium (VI) which are generally used in the surface of the inclusions are generally comprised of sources of chromium (III) ions and one or more mismatches which are known to those skilled in the art. The treatment solution is generally less than 2. In the two steps of the method of the invention, the <RTI ID=0.0>>>>>> Suitable complexing agents are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentane = hexanoic acid, cyclopentaic acid, ethyl hydrazide salicylic acid, formic acid, succinic acid, 3,5- Dinitrobenzoic acid, tetrahydrofuran_2_decanoic acid, sorbus 147617.doc 201042082 Acidic acid mash, malonic acid, claric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , azelaic acid, maleic acid, phthalic acid, terephthalic acid, ethylenediazotetraacetic acid, ethylenediaminetetraacetic acid, diethylenediamine-5=acid, nitrogen triacetic acid, tartaric acid, lemon Acid, iso-citric acid, malic acid, ascorbic acid, lactic acid, gluconic acid, glucuronic acid, gallic acid, alcohol, ethanol, 1-propanol '2-propanol, 1-butanol, 2-butanol , pentanol, propanol, propanol, ethylene glycol butyl ether and glycol ether. The content of all the complexing agents in each of the two treatment solutions is from 0.75 to 200 g/b, preferably from 5 to 1 g/丨, most preferably from 1 to 5 g/1. When the surface to be treated is composed of zinc or a zinc alloy, the two treatment solutions comprise 3 water-soluble zinc compounds each of 0.75 to 200 mmol/1, preferably 3 to 100 axes/1, most preferably 10 to 40 mmol/b When the surface to be treated is composed of magnesium or a magnesium alloy, the two treatment solutions include water-soluble magnesium compounds each having a content of 2 to 210 mmol/1, preferably 8 to 75 mm〇l/ Preferably, it is 12 to 40 mmol/b. When the surface to be treated is composed of aluminum or an aluminum alloy, the two treatment solutions include water-soluble aluminum compounds each having a content of 1.8 to 185 mmol/1, preferably 7.5 to 85. The optimum of mmol/1' is η to 40 mmol/1. The two baths of the treatment steps 1 and 2 optionally include a source of fluoride ions selected from the group consisting of NaF, KF, NH4F, NaHF2, KHF2 and NH4HF2. The fluoride ion is added in an amount of 0.001 to 10 g/?, preferably 0.01 to 5 g/? and most preferably 0.05 to 2 g/?. The two baths of the treatment steps 1 and 2 optionally include a source of gas ions selected from the group consisting of Naa, KC1 and ΝΗβι. The chloride ion is added in an amount of g 〇ι to 147617.doc -10- 201042082 • 20 gA, preferably 〇.1 to 10 g/丨 and most preferably 〇 5 to 5 g/1. • Another optional component of the two baths of steps 1 and 2 is a sulphate compound, and at least one phosphate compound is selected from the group consisting of: orthophosphoric acid, polyphosphoric acid, metaphosphoric acid, such acids a salt, an ester of such an acid having an organic group of up to 12 carbon atoms, and a mixture of such compounds. The phosphorus and acid salt compounds are added in an amount of from 55 to 100 g/Ι, preferably from 3 to 50 g/Ι and most preferably from 5 to 20 g/I. 0 is at least one metal or metalloid selected from the group consisting of Sc, Y, Ti, Zr, Mo, W, Μ, Fe, Co, Ni, Zn, B, A, Si, in order to increase the corrosion protection.丨 and 2 are added to the two treatment solutions as needed. The # element may be in the form of its salt or in the form of a chiral anion or a corresponding acid of the anion (for example, hexafluoroboric acid, hexafluoroantimonic acid, hexafluoroantimonic acid or hexafluorozirconic acid, tetrafluoroboric acid or hexafluorophosphoric acid). Or in the form of a salt thereof. The method of the invention can be used in very many passivation systems. When the soluble cobalt salt is added to each of the treatment steps ❹ and 2 at a content of from 0. 2 to 3 g/1 (preferably g/1), an excellent corrosion protection value of black passivation can be achieved. - For post-treatment, the substrate which has been taken from the treatment solution 2 is dried without further washing as before. For example, 'drying can be done in a drying drum. The residue of the treatment solution 2 attached to the drying drum can be removed by means of a thermal solution. EXAMPLE An aqueous reaction solution having the following composition was prepared: The reaction solution used in Step 1: 147617.doc 201042082 at 74 weight. /. 3 61 g/1 of Cr(III) ion, 10.9 g/1 of phosphate ion, 25 g/1 of zinc ion, 12.1 g/Ι of gluconic acid, in the form of a strength chromium (III) nitrate solution, 1 〇 tartaric acid, 〇〇88 吕 with fluoride ion and 1.22 g / Ι gas ion. The pH of the solution was set to 1.8 by nitric acid. Reaction solution for step 2: 3 6 i g / i of Cr(III) ion, 10.9 g / 1 of phosphate ion, 25 g / 1 of 74 wt% strength chromium nitrate (111) solution Zinc ion, gluconic acid of i2.i gn, tartaric acid of ίο g/i, fluoride ion of 〇〇88笆8 and chloride ion of 1_22 g/ι. The pH of the solution was set to 4 by sodium hydroxide. Acidic electrolyte (trade name: obtained from At〇tech DeuW-nd
GmbH之Unizink NCZ 420)中使鋼元件塗覆有i〇 厚之辞 層。然後，於2(TC下，使該鋼元件浸入石肖酸/水混合物（約 〇_2%之HN〇3)中10 s以得到表面。隨後，利用去礦物質水 清洗該部件且於饥下，立即浸入如上述製得之反應溶液 1中40 s。在無進一步之清洗步驟下，接著，於贼下，使 該部件立即浸人如上述製得之反應溶液2〇5s。在令處理 溶液滴完之後’在無最终之清洗步驟下，使該部件於 120°C下進行乾燥15分鐘。 在根據卿雙丨SS之歸試驗中，表面保料變細h， 顯示5%之僅僅在 h後之白錢腐敍及僅僅在多於刪h 後之紅錄腐姓。藉由本發明之方法實現之腐㈣護係至少 與藉由先前技術所習知之方法實現之腐触保護一樣佳，不 1476l7.doc •12· 201042082 ' 同的係，在本發明之方法中，污染有重金屬之廢水量明顯 _ 減少。In the Unizink NCZ 420) of GmbH, the steel elements are coated with layers of thickness. Then, at 2 (TC), the steel component was immersed in a sulphuric acid/water mixture (about %2% of HN〇3) for 10 s to obtain a surface. Subsequently, the component was washed with demineralized water and was hungry. Immediately, immersed in the reaction solution 1 prepared as described above for 40 s. In the absence of further washing steps, and then under the thief, the part was immediately immersed in the reaction solution prepared as described above for 2 〇 5 s. After the solution was dripped, the part was dried at 120 ° C for 15 minutes without a final cleaning step. In the test according to the double 丨 SS, the surface maintenance material became fine h, showing 5% only in After the h, the white money is rotted and only more than the red record of the h. The rot (4) system achieved by the method of the present invention is at least as good as the corrosion protection achieved by the method known in the prior art. No. 1476l7.doc •12· 201042082 'The same system, in the method of the present invention, the amount of waste water contaminated with heavy metals is significantly reduced.
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