201139736 六、發明說明： 【發明所屬之技術領域】 本發明疋有關於一種不銹鋼表面處理液，特別是指一 種不錄鋼表面本色白化處理製程所使用之處理液。本^明 另有關於-種使用本發明該處理液的不錄鋼表面本色 處理製程。 【先前技術】201139736 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a stainless steel surface treatment liquid, and more particularly to a treatment liquid used for a natural whitening treatment process for a non-recorded steel surface. The present invention relates to a non-recording surface natural color processing process using the treatment liquid of the present invention. [Prior Art]
不銹鋼具有獨特的強度、較高的耐磨性、優越的防腐 性能及不易生錄等優良的特性，而不錄鋼的表面處理技術 的發展程度對於錢鋼的應用與開發往往具有極大的影響， 表面處理可定義為不錄鋼於塗裝前的被塗面整理作業，其 的為除去破壞塗膜因素與腐μ性物質，包括灰塵、動植 物油、礦油等附著物以及鋼鐵本身產生之鐵錄等。基本上 ，不錄鋼是鐵與鉻(Cr)的合金，除了鉻元素外，還因含有鎳 (NO、碳(C)、峨。)、鈦(Ti)、钶(Ac)、砸剛而成為不 同類的不錄鋼’ 一般常見的不錄鋼則是有鉻不錄鋼（絡含量 為12%以上）及錄鉻不錄鋼（鉻含量約為，鎳 12%)。 ” 里、兩 因為不錄鋼在加工過程中，會經過卷板、札邊、焊接 或者經過人工表面火烤加溫處理等，而產生黑色氧化皮[即 黑皮（nnU _)]’這種堅硬的黑皮除了是由數種氧化鐵所 組成二卜’還包含了録及鉻等成分之氧化物，對於尚需進 仃下-道工序加工的不銹鋼材而言，能即時而有效地去除 其表層上的黑皮’可順利進行下道卫序加工、防止工件表 201139736 面的腐姓、保持表面之光澤並延長所製得零件之壽命。此 ，去除黑皮之不錢鋼表面本色白化處理，傳統上為採用氣 氟酸(HF)和硝酸(ΗΝ〇3)進行強腐蝕之酸洗方法，但這種方 法因係採用強酸溶液浸蝕代處理之鋼材’故在設備上會有 所限制’在製程中更可能會因為產生二氧化氮⑽2)氣體及 HF蒸氣而對人體有害且污染環境，此酸洗方法的腐钱性強 且無選擇性，在浸蝕過後對於底材往往造成侵蝕，而使得 處理後的不銹鋼材表面不平滑。 基於不銹鋼線材製程之考量與日趨重要的綠色工業製 程對於環境的適性，不銹鋼表面本色白化處理製程以及其 所使用的處理液便亟需加以研究與開發，以增進本領域產 業的永續經營與發展。 【發明内容】 於是，本發明之第一目的，即在提供一種不銹鋼表面 本色白化處理製程所使用之處理液，其ρΗ值是大於7，且 包含：水、一含氯離子之化合物以及一螯合劑，其中，該 螯合劑是擇自於-有機胺、—有機酸、—有機酸鹽、一醋 、一醣之衍生物，或此等之一組合。 本發明之第二目的，即在提供一種不銹鋼表面本色白 化處理製程，其係將一欲進行表面本色白化處理之不錄鋼 材浸覆於前述本發明之處理液中，且以該不銹鋼材作為一 陽極予以通電，以使得該不銹鋼材表面之黑皮鬆脫。 【實施方式】 下將再就本發明之二 除了以上所述之各基本要件，以 201139736 目的，提供其他技術上之建議與說明。 ' 較佳地，該螯合劑是螯合力偏弱的配位子且最終不影 響氫氧根與不銹鋼銹皮產生沉澱物者，譬如檸檬酸（Citric Acid)，如此可易於維持藥水的循環使用。 較佳地，除檸檬酸外，適用作為本發明螯合劑之有機 酸還包括一胺基酸，譬如乙烯二胺四乙酸 (Ethylenediaminetetraacetic Acid 簡稱 EDTA)、甘胺酸 (Glycine)，或此等之一組合。 φ 較佳地，適用作為本發明螯合劑之醣是葡萄糖、蔗糖 ，或此等之一組合。 選擇性地，該螯合劑是一呈鹼性之螯合劑，且是擇自 於一多胺、一醇胺、一醇胺之衍生物、一 St之衍生物、一 - 醇酸鹽，或此等之一組合。 較佳地，該多胺是二乙三胺、三乙四胺、六乙四胺， 或此等之一組合。 較佳地，該醇胺是單乙醇胺、雙乙醇胺、三乙醇胺， • 或此等之一組合。 較佳地，該醇胺之衍生物是氮氧陸圜（Morpholine)。 較佳地，該St之衍生物是葡萄糖酸鈉。 較佳地，該醇酸鹽是乳酸鹽、酒石酸鹽、檸檬酸鹽， 或此等之一組合。 較佳地，該pH值大於7係經由使用一呈驗性之螯合劑 來達成，或是該處理液更包含一用於調整pH值的鹼化劑來 達成。該呈驗性之螯合劑之選擇係如前述。 201139736 較佳地，該鹼化劑是擇自於一金屬氫氧化物、一金屬 弱酸鹽，或此等之一組合，且該金屬氫氧化物與金屬弱酸 鹽中之金屬是擇自於鋰、鈉、鉀、的或鋇。 較佳地，該處理液之pH值是介於8 〇〜13 〇之間。 較佳地，該含氣離子之化合物的濃度是介於丨〇 g/L至 250 g/L 之間。 較佳地，該含氣離子之化合物是擇自於鹼金屬之氣化 物、鹼土金屬之氣化物、銨之氣化物，或此等之一組合。 較佳地’該螯合劑的濃度是介於〇 5 g/L至1〇〇 g/L之 間’更佳是介於10 g/L至20 g/L之間。 較佳地，該處理液還包含一濕潤劑。濕潤劑之功能主 要是降低水的表面張力’使溶液有較佳的滲透效果，只要 能降低表面張力並與處理液之其他組份相容，皆適用於本 發明。較佳地’該濕潤劑是改質的非離子型界面活性劑。 在本發明之一具體例中，該濕潤劑是奇佳化學所提供之型 號為1241者。 較佳地’該濕潤劑的濃度是介於0.2 g/L至〇.5g/L之間 〇 有關本發明製程達到使黑色銹皮鬆脫目的之機制推測 為：黑色銹皮基本上為Ni、Cr或Fe之2-3價氧化物，可 藉由陽極被氧化產生的CL前驅物與〇2前驅物腐蝕鬆動， 再進一步與溶液中之氫氧根產生沉澱物，而陰極生成的氣 氧根則可維持溶液的平衡，故淨反應應可表示成： MOx + h2〇 ^ MOx(OH) j + 1/2 H2 201139736 基於前述推測之機制’本發明處理液因為是處於鹼性 條件，因此主要是在陽極產生cl2的前驅物來使黑色銹皮鬆 脫，而可避免產生有非所欲味道的cl2〇 較佳地’本發明不銹鋼表面本色白化處理製程中通電 所施加之電流密度是介於5 A/dm2至4〇 A/dm2之間。 較佳地，本發明不銹鋼表面本色白化處理製程於通電 時之處理液溫度是介於5°C至8〇t之間。在本發明之各具 體例中，通電時之處理液溫度是介於2〇。〇至之間。 以下將以實施例來說明本發明處理液之配製及使用該 處理液之製程，並配合比較例來說明本發明處理液及製程 之功效。若無特別交代，實施例之製備及後續之各項測試 與評估，皆是在常溫常壓的環境下進行。須注意的是，該 實轭例僅為例示說明之用，而不應被解釋為本發明實施之 限制。 化學品及付料 1. 濕潤劑：購自奇佳化學公司，型號為1241。 2. 以下實施例及比較例所使用之化學品除食鹽為市售且濕 潤劑如上述之外，其餘皆為購自第一化工試藥級藥品。 3. 不鏽鋼材：其材質為酸洗前黑皮不銹鋼，5.5 直徑線 材’由華新麗華公司提供’型號為304及316。 <實施例與比較例> 實施例1 -9及比較例1 _3 A.不銹鋼表面本色白化處理製程所使用之處理液的製備 所有實施例與比較例之處理液的成份、濃度及pH值 201139736 係如表-所示’其中所有實施例與比較例皆是以水為溶劑來 進行配置。 B. 不錄鋼表面本色白化處理製程 除比較例3為單純酸洗且未通電外，其餘各實施例與 ^較例係將304及316二種型號之不錄鋼材浸覆於A.中已 裝備而得之各實施例與比較例的處理液中，且以該等不銹鋼 材作為—陽極分別予以通電以使得該等不錄鋼材表面之黑 皮脫’纟中’各實施例與比較例在實施此製程日夺，處理液 之溫度會由室溫逐漸升高，溫度範圍是介於2〇。匚至之 間’通電所施加<電流密度及操作時間亦列於表一中。 C. 功效測試 目視方式對前述各實施例及比較例製程所得 各不錄鋼材進行‘累色錄纟鬆脫效果之評#，其結果列於表 曰中其中’鬆脫效果極佳是以「◎」表示；鬆脫效果佳Stainless steel has unique strength, high wear resistance, superior corrosion resistance and excellent characteristics such as easy to record. The development degree of surface treatment technology without recording steel often has a great influence on the application and development of Qiangang. The surface treatment can be defined as the unfinished steel surface to be coated before the coating, which is to remove the damage of the coating film and the septic substances, including dust, animal and vegetable oil, mineral oil and other deposits and iron produced by the steel itself. Record and so on. Basically, non-recorded steel is an alloy of iron and chromium (Cr). In addition to chromium, it also contains nickel (NO, carbon (C), niobium), titanium (Ti), niobium (Ac), niobium. Become a different type of non-recorded steel 'Generally common non-recorded steel is chromium non-recorded steel (complex content of 12% or more) and recorded chromium non-recorded steel (chromium content is about, nickel 12%). "In the middle, because the steel is not recorded in the process, it will be subjected to coiling, edging, welding or artificial surface baking and heating, etc., resulting in black scale (ie black skin (nnU _)]' The hard black skin is composed of several kinds of iron oxides. It also contains oxides of chromium and other components. It can be used instantly and effectively for stainless steel materials that need to be processed in the next process. Remove the black skin on the surface of the 'can smoothly carry out the next line of processing, prevent the surface of the workpiece table 201139736 surface, maintain the surface gloss and extend the life of the parts produced. This, remove the black skin of the steel surface Whitening treatment, which is traditionally a pickling method using strong corrosive acid (HF) and nitric acid (ΗΝ〇3), but this method is based on the steel treated by strong acid solution etching, so it will be on the equipment. Restriction 'more likely to be harmful to the human body and pollute the environment due to the production of nitrogen dioxide (10) 2) gas and HF vapor in the process. This pickling method is highly corrosive and non-selective, and often causes erosion on the substrate after etching. And make The surface of the stainless steel material is not smooth. Based on the consideration of the stainless steel wire process and the increasingly important green industrial process, the environmental whiteness of the stainless steel surface and the treatment liquid used in the stainless steel surface need to be researched and developed. The invention aims to improve the sustainable operation and development of the industry in the field. Accordingly, the first object of the present invention is to provide a treatment liquid for a stainless steel surface natural whitening treatment process, which has a value of ρ 大于 greater than 7, and includes: Water, a chloride ion-containing compound, and a chelating agent, wherein the chelating agent is selected from the group consisting of an organic amine, an organic acid, an organic acid salt, a vinegar, a sugar derivative, or a combination thereof. A second object of the present invention is to provide a stainless steel surface natural whitening process for immersing a non-recorded steel material to be surface-whitened in the treatment liquid of the present invention, and using the stainless steel material. The anode is energized as an anode to loosen the black skin on the surface of the stainless steel. [Embodiment] For the basic elements mentioned above, other technical suggestions and explanations are provided for the purpose of 201139736. ' Preferably, the chelating agent is a weakly chelated ligand and ultimately does not affect the production of hydroxide and stainless steel scale. The precipitater, such as Citric Acid, can easily maintain the recycling of the syrup. Preferably, in addition to citric acid, the organic acid suitable as the chelating agent of the present invention further comprises an amino acid such as ethylene diamine. Ethylenediaminetetraacetic acid (EDTA), glycine (Glycine), or a combination of these. φ Preferably, the sugar suitable as the chelating agent of the present invention is glucose, sucrose, or a combination thereof. The chelating agent is an alkaline chelating agent and is selected from the group consisting of a polyamine, a monolamine, a derivative of an alcoholamine, a derivative of St, an alkoxide, or the like. A combination. Preferably, the polyamine is diethylenetriamine, triethylenetetramine, hexaethylenetetramine, or a combination thereof. Preferably, the alkanolamine is monoethanolamine, diethanolamine, triethanolamine, or a combination thereof. Preferably, the derivative of the alkanolamine is moroxiline. Preferably, the derivative of St is sodium gluconate. Preferably, the alkoxide is lactate, tartrate, citrate, or a combination of these. Preferably, the pH greater than 7 is achieved by the use of a chelating agent which is illustrative, or the treatment fluid further comprises an alkalizing agent for adjusting the pH. The choice of such a chelating agent is as described above. 201139736 Preferably, the alkalizing agent is selected from a metal hydroxide, a metal weak acid salt, or a combination thereof, and the metal hydroxide and the metal weak acid salt are selected from Lithium, sodium, potassium, or cesium. Preferably, the pH of the treatment liquid is between 8 〇 and 13 〇. Preferably, the concentration of the gas ion-containing compound is between 丨〇 g/L and 250 g/L. Preferably, the gas ion-containing compound is selected from the group consisting of an alkali metal gasification, an alkaline earth metal gasification, an ammonium gasification, or a combination thereof. Preferably, the concentration of the chelating agent is between 〇 5 g/L and 1 〇〇 g/L, more preferably between 10 g/L and 20 g/L. Preferably, the treatment liquid further comprises a humectant. The function of the humectant is mainly to lower the surface tension of the water to make the solution have a better penetration effect, as long as it can reduce the surface tension and is compatible with the other components of the treatment liquid, and is suitable for use in the present invention. Preferably the humectant is a modified nonionic surfactant. In one embodiment of the invention, the humectant is a model of 1241 supplied by Qijia Chemical. Preferably, the concentration of the humectant is between 0.2 g/L and 〇.5 g/L. The mechanism for achieving the purpose of loosening the black rust skin according to the process of the present invention is presumed to be: the black scale is substantially Ni, The 2-3 valence oxide of Cr or Fe can be corroded by the CL precursor generated by oxidation of the anode and the precursor of ruthenium 2, and further precipitates with hydroxide in the solution, and the gas radical formed by the cathode The balance of the solution can be maintained, so the net reaction should be expressed as: MOx + h2〇^ MOx(OH) j + 1/2 H2 201139736 Based on the above-mentioned speculative mechanism, the treatment liquid of the present invention is mainly in alkaline condition, so The precursor of cl2 is generated at the anode to loosen the black scale, and the cl2 which has an undesired taste can be avoided. Preferably, the current density applied by the current in the whitening treatment process of the stainless steel surface of the present invention is 5 A/dm2 to 4〇A/dm2. Preferably, the temperature of the treatment liquid of the stainless steel surface of the present invention is between 5 ° C and 8 ° t when the power is applied. In each of the specific embodiments of the present invention, the temperature of the treatment liquid at the time of energization is 2 Torr. Between the two. Hereinafter, the preparation of the treatment liquid of the present invention and the process of using the treatment liquid will be described by way of examples, and the effects of the treatment liquid and the process of the present invention will be described with reference to comparative examples. Unless otherwise specified, the preparation of the examples and subsequent tests and evaluations are carried out under normal temperature and pressure conditions. It is to be understood that the simplifications are for illustrative purposes only and are not to be construed as limiting. Chemicals and materials 1. Wetting agent: purchased from Qijia Chemical Company, model number 1241. 2. The chemical salt used in the following examples and comparative examples is commercially available and the humectant is as described above, and the others are purchased from the first chemical reagent grade drug. 3. Stainless steel: The material is black leather before pickling, 5.5 diameter wire is supplied by Huaxin Lihua Company, models 304 and 316. <Examples and Comparative Examples> Examples 1 to 9 and Comparative Example 1 _3 A. Preparation of Treatment Liquid for Natural Color Whitening Treatment Process of Stainless Steel Surface Composition, Concentration, and pH Value of Treatment Liquids of All Examples and Comparative Examples 201139736 is shown in Table - 'All of the examples and comparative examples are configured with water as a solvent. B. Non-recorded steel surface natural whitening process except that the comparative example 3 is pure pickling and is not energized, the other examples and the comparative examples are 304 and 316 two types of non-recorded steel are immersed in A. In the treatment liquids of the respective examples and the comparative examples, the stainless steel materials were respectively used as the anodes, and the anodes were respectively energized so that the black skins of the unrecorded steel sheets were removed from each other. In the implementation of this process, the temperature of the treatment liquid will gradually increase from room temperature, and the temperature range is 2〇. The current application and current density and operating time are also listed in Table 1. C. Efficacy test visual method The evaluation results of the 'retraction color release effect' were obtained for each unrecorded steel obtained in the above-mentioned respective examples and comparative examples, and the results are listed in the table, where the 'loose effect is excellent is " ◎" indicates that the loosening effect is good
疋以〇」表示；鬆脫效果不佳是以「X」表示，幾乎盔輕 脫效果是以「xy志- 、A Λ入」衣不0 201139736 表一疋 〇 〇 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
編號 處理液（aq) pH 值 操作餐 Η牛 功效測試 含氯離子之 化合物 螯合劑 驗化劑 濕潤劑 電流 密度 (A/ dm2) 操作 時間 (sec) 304 除 黑皮 效果 316 除 黑皮 效果 種類 濃 度 (g/L) 種類 濃 度 (g/L) 種類 濃 度 (g/L) 種類 濃 度 (g/L) 實 施 例 1 NaCl 100 單乙醇 胺 20 - - 1241 0.5 8 20 60 ◎ 〇 2 NaCl 150 濘檬酸 15 NaOH 20 1241 0.2 11 20 60 ◎ ◎ 3 NaCl 200 二乙三 胺 20 KOH 10 - - 13 30 40 ◎ ◎ 4 NaCl 200 葡萄糖 酸鈉 20 NaOH 10 1241 0.2 13 30 60 ◎ ◎ 5 NaCl 250 甘胺酸 10 KOH 5 - - 10 20 60 ◎ ◎ 6 KC1 ISO 單乙醇 胺 20 - - 1241 0.5 8 20 60 ◎ ◎ 7 KC1 100 葡萄糖 20 KOH 20 - - 13 30 120 ◎ ◎ 8 NH4C1 200 單乙醇 胺 20 NaOH 20 8 30 60 ◎ ◎ 9 NaCl 200 EDTA 10 NaOH 20 - - 13 20 60 ◎ ◎ 比 較 例 1 NaN03 200 單乙醇 胺 20 - - 1241 0.5 8 20 60 XX XX 2 Na2S04 200 單乙醇 胺 20 - - 1241 0.5 8 20 60 XX XX 3 hn〇3 100 HF 50 未通電 60 XX XXNo. treatment solution (aq) pH value operation yak efficacy test chloride ion-containing compound chelating agent test agent humectant current density (A / dm2) operation time (sec) 304 black skin effect 316 black skin effect type concentration (g/L) Species concentration (g/L) Species concentration (g/L) Species concentration (g/L) Example 1 NaCl 100 Monoethanolamine 20 - - 1241 0.5 8 20 60 ◎ 〇2 NaCl 150 Citric acid 15 NaOH 20 1241 0.2 11 20 60 ◎ ◎ 3 NaCl 200 Diethylenetriamine 20 KOH 10 - - 13 30 40 ◎ ◎ 4 NaCl 200 Sodium gluconate 20 NaOH 10 1241 0.2 13 30 60 ◎ ◎ 5 NaCl 250 Glycine 10 KOH 5 - - 10 20 60 ◎ ◎ 6 KC1 ISO monoethanolamine 20 - - 1241 0.5 8 20 60 ◎ ◎ 7 KC1 100 Glucose 20 KOH 20 - - 13 30 120 ◎ ◎ 8 NH4C1 200 Monoethanolamine 20 NaOH 20 8 30 60 ◎ ◎ 9 NaCl 200 EDTA 10 NaOH 20 - - 13 20 60 ◎ ◎ Comparative Example 1 NaN03 200 Monoethanolamine 20 - - 1241 0.5 8 20 60 XX XX 2 Na2S04 200 Monoethanolamine 20 - - 1241 0.5 8 20 60 XX XX 3 hn〇3 100 HF 50 not powered 60 XX XX
由表一可看出，相較於比較例1 -3幾乎無鬆脫效果之情形， 本發明各實施例之處理液藉由含氣離子之化合物所釋放之氣 離子，配合鹼性條件及螯合劑與濕潤劑之使用，在對於表面 有黑色銹皮的不鏽鋼材施予陽極通電處理後，確實使得不鏽 鋼材產生極為優異之黑色銹皮鬆脫效果，此結果也驗證了前 述所推測機制中強調之氯離子搭配陽極處理之重要性 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利範 201139736 圍及發明說明内容所作之簡單的等效變化與修飾，皆仍屬本 發明專利涵蓋之範圍内。 【圖式簡單說明】 (無）It can be seen from Table 1 that the treatment liquid of each embodiment of the present invention is combined with the alkaline condition and the chelate by the gas ions released by the gas ion-containing compound in comparison with the case of the comparative example 1-3. The use of a mixture and a humectant, after applying an anodic elective treatment to a stainless steel material having a black scale on the surface, does result in an excellent black rust release effect of the stainless steel material, and the result also confirms the emphasis in the aforementioned mechanism. The importance of the chloride ion combined with the anode treatment is only the preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, that is, the patent application model 201139736 and the invention description are applicable. The simple equivalent changes and modifications made by the content are still within the scope of the invention. [Simple description of the diagram] (none)
10 201139736 【主要元件符號說明】 (無）10 201139736 [Description of main component symbols] (none)
1111