TW552318B

TW552318B - Cleaning agents and methods for aluminum or aluminum alloy

Info

Publication number: TW552318B
Application number: TW090129235A
Authority: TW
Inventors: Kazuya Hino; Yasuaki Iino; Kazuya Tanaka
Original assignee: Nihon Parkerizing
Priority date: 2000-12-06
Filing date: 2001-11-27
Publication date: 2003-09-11
Also published as: JP2002173785A; KR20020045548A; JP3932245B2

Abstract

The present invention provides a cleaning agent for aluminum or aluminum alloy after forming process and a cleaning method using the cleaning agent. The cleaning agents preferably contain at least one alkaline component (builder) selected from alkali metal hydroxide, inorganic phosphate and carbonate at 0.5-50.0 g/L, vanadic compound containing vanadium atoms of 0.01-10 b/L, and surfactants at 0.1-10 b/L, and have pH of 9.0-13.0. The cleaning methods comprise the steps of heating the cleaning agents to 30-80 DEG C, and allowing the surface of aluminum or aluminum alloy to contact with the cleaning agents for at least 2 seconds by means of spraying or immersion.

Description

552318 Λ7 B7 五、發明說明（【發明之詳細說明】【發明所屬技術領域】一般而言，銘及紹合金等金屬材料係經熱加工、冷型ί二最後依目的之不同，進行表面處、或主衣“驟。在金屬材料進行各種加工成型後，於進各種表面處理及塗裝工程前，必須進行洗淨處理。本係關於用作洗淨狀洗淨液、及制本洗淨劑之洗淨^ 法。【習知技術】訂線々、一般而言，鋁及鋁合金等金屬材料係經熱加工、冷加工等各種成型加卫。例如，減紹合金容器#通皆採^被稱為抽拉（drawing)、壓平（lroning)之擠壓及成型操作，所製造得來。根據本操作，容器表面上由於添加了潤滑劑，殘留之鋁碎屑會黏附於表面上。此種污染物質會對金屬材料之後績處理，例如表面處理或塗裝處理等造成不良影響。因此之故，必須進行洗淨處理，將此類污染物質=金屬表面徹底清除。此時，洗淨力的優劣將不但能提升金屬材料外觀之美觀性，亦會對表面處理度或塗裝時之密合度濟部智慧財產局員工消費合作社印製等造成影響。此種金屬材料之洗淨係為適用於對金屬加工油、防鏽油等油狀污垢、或加工時所產生之金屬粉末、塵埃等個體污染進行適度的钱刻（etchi ng)，以進行洗淨之用 '。具有良好的防止鋁或鋁合金表面產生黑色污點（smut)之功能，並能提供適合於洗淨後進行合成處理或塗裝之表面狀本紙張尺度適用中國國豕標準（CNS)A4規格（21〇 X 297公爱 552318 A7 五、發明說明（您之銘或銘合金表面用驗性洗淨液為其理想。又，經成型處理之鋁製容器其表面處理程序一般係為：脫脂一水洗一合成一水洗一乾燥；然而，亦有省略八成處理，直接以水洗代替之情況。在此種場合，由於經脫脂一水洗後乾燥時，形狀物之液體積存部分會產生變^等 ^題。又，生產線上由於生產的狀況，也可能導致滯留之情形。在此滯留之生產線内，物體於各工程内滯留時，由於洗淨不均勻，會產生外表不美觀之問題。並未提Z對此類，燥時之變色問題及滯留時所導致外觀不良進行解決之對策。訂又，例如特開昭56-136978號公報中，揭示出一種發明，以合成處理為目的，含有釩化合物離子〇〇〇5摩爾 /L以上之濃度，可形成具有良好耐蝕性之皮膜。然而手p 本經揭示出之發明，並無法對銘及铭合金表面進行洗淨處理、亦或污染物質之清除。曰線【發明欲解決之課題】本發明係以上述之情況為鑑，因應上述之需要，解決上述以習之技術為基礎之問題為目的。提供—種= j淨液及使用此種洗淨液之方法，適合於紹或紹二屬材料於熱加工、冷加工等成型加工後之所進行之洗^ 進行成型加工後之表面處理或塗裝等處i 【解決課題之方法】552318 Λ7 B7 V. Description of the invention ([Detailed description of the invention] [Technical field to which the invention belongs] Generally speaking, metal materials such as Ming and Shao alloys are hot-processed and cold-formed. Finally, according to the purpose, surface treatment, Or the main coat. "After the metal materials are processed and shaped, they must be cleaned before they are subjected to various surface treatments and coating projects. This series is used as a cleaning liquid and a detergent Washing method. [Knowledge technology] Threading, generally speaking, metal materials such as aluminum and aluminum alloys are reinforced by various processes such as hot working and cold working. For example, 少绍合金罐 # 通都采 ^ 被It is manufactured by extrusion and molding operations called drawing and lroning. According to this operation, the residual aluminum debris will adhere to the surface due to the lubricant added to the surface of the container. This This kind of pollutants will adversely affect the subsequent processing of metal materials, such as surface treatment or coating treatment. Therefore, it is necessary to perform cleaning treatment to completely remove such pollutants = metal surface. This At the same time, the strength of the cleaning power will not only improve the aesthetics of the appearance of the metal materials, but also affect the surface treatment or the degree of closeness when painting. The printing of the consumer consumer cooperatives of the Ministry of Intellectual Property Bureau of Jibei will affect. Washing is suitable for etchi ng suitable for oily dirt such as metal processing oil, rust-proof oil, or individual pollution such as metal powder and dust generated during processing. It has a good function of preventing black smut on the surface of aluminum or aluminum alloy, and can provide a surface shape suitable for synthetic treatment or painting after washing. This paper is applicable to China National Standard (CNS) A4 specifications (21 〇X 297 Gongai 552318 A7 V. Description of the invention (It is ideal to use an inspection cleaning solution on the surface of your inscription or inscription alloy. In addition, the surface treatment procedure of the aluminum container after forming treatment is generally: degreasing, washing, and washing. The synthesis is washed with water and dried; however, there is also a case where the 80% treatment is omitted and the washing is directly replaced. In this case, the shape of the object is changed after drying after degreasing and washing with water. Changes in the liquid storage part may cause problems such as ^. Moreover, due to the production conditions on the production line, it may also cause detention. In this detention production line, when objects are detained in various projects, due to uneven washing, it may occur. The appearance is not beautiful. There is no mention of Z to deal with such problems, such as the problem of discoloration during dryness and the appearance of the poor appearance during staying. The invention is disclosed in, for example, Japanese Patent Laid-Open No. 56-136978. For the purpose of synthetic treatment, containing vanadium compound ion at a concentration of more than 0.05 mol / L can form a film with good corrosion resistance. However, the invention disclosed by the hand cannot clean the surface of the inscription and the inscription alloy. Clean treatment, or the removal of polluting substances. Line [Problems to be Solved by the Invention] The present invention is based on the above-mentioned situation, and in response to the above-mentioned needs, solves the above-mentioned problems based on the conventional technology for the purpose. Provide—kind = j cleansing liquid and the method of using this cleaning liquid, suitable for washing of Shao or Shao two genus materials after hot working, cold working, etc. ^ Surface treatment or coating after forming processing Waiting place [Method for solving problem]

亦即’本發明係為-種驗性洗淨液，以含有G 本紙張尺度顧巾目 552318 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（）金屬鹽、酒石酸鹼金屬鹽、或山梨糖醇（s〇rbit〇i);至少任選以上賴之化合物，料料屬料射貞劑，盘洗淨劑加以配合。㈣屬離子封鎖劑含有量係為Q. 11〇為 /L’·若未達％〇· i g/L ’則於進行紹之洗淨時，導致呈表面所溶出之轉子螯化（ehelate)力不足，易使侧、力及去污力降低，並不理想。反之，即使超過1(). Q g八，其效果也因已呈飽和狀態而無法加以提升。 —本發明之鹼性洗淨液係使用浸泡或喷霧法，使其附者於紹或IS合金之表面上。此時，空氣中所含之碳酸氣血鹼性成分中和，會使PH值下降，鹼性洗淨液之邱值為 9. 0〜13. 0，理想狀態則必須保持於1〇. 5 n. 5之範圍内。若未達到9· G’則會由於㈣不足，使得銘表面產生不均勻之現象’且無法徹底清除附著於金屬表面之污點。反之，若高於PH13.0,則會由於蝕刻過度，導致微量之黑色汙點之產生，降低合成後之耐飯性。又，本發明之驗性洗淨液係使用浸泡或噴霧法，使其附著於鋁或鋁合金之表面上進行洗淨處理。此時，將鹼性洗淨液加溫至30〜8(rc，理想之狀態則為加溫至仙〜川 c。使本經加溫之洗淨液與鋁或鋁合金表面接觸2秒以上’理想之狀態則為使其接觸2〜60秒。【實施例】以下將同時舉出幾個實施例及比較例，以對本發明之，果進行更為具體之說明。所使用之實驗材料、實驗條件、實驗方法如下所述。 7That is, the present invention is a kind of inspection cleaning liquid, which is printed with G paper size 552318, printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. A5. Description of the invention () Metal salt, tartrate alkali metal salt, Or sorbitol (sorbitOi); at least any one of the above compounds is selected. The content of genus ion blocking agent is Q. 11 ° is / L '. If it does not reach% 0. ig / L', it will cause the rotor to chelate on the surface when it is washed. Insufficient, easy to reduce the side, force and detergency, is not ideal. Conversely, even if it exceeds 1 (). Q g, its effect cannot be improved because it is already saturated. — The alkaline cleaning solution of the present invention is immersed or sprayed on the surface of Shao or IS alloy. At this time, the carbonic acid, blood, and alkaline components contained in the air are neutralized, which will reduce the pH value. The Qiu value of the alkaline cleaning solution is 9. 0 ~ 13.0, and the ideal state must be maintained at 10.5. n. within the range of 5. If it does not reach 9 · G ’, it will cause unevenness on the surface of the surface due to insufficient ㈣, and it is impossible to completely remove the stains attached to the metal surface. Conversely, if it is higher than PH13.0, a small amount of black stains will be generated due to excessive etching, which will reduce the rice resistance after synthesis. In addition, the inspection cleaning solution of the present invention is made to adhere to the surface of aluminum or an aluminum alloy by a immersion or spray method for cleaning treatment. At this time, the alkaline cleaning solution is warmed to 30 ~ 8 (rc, ideally, it is heated to cents ~ chuan c. Make the heated cleaning solution contact the aluminum or aluminum alloy surface for more than 2 seconds. The state is to allow it to contact for 2 to 60 seconds. [Examples] Several examples and comparative examples will be listed below in order to more specifically explain the results of the present invention. Experimental materials and experimental conditions used The experimental method is as follows.

ft衣--------II------、——線丨秦 (請先閱讀背面之注意事項再填寫本頁) ϋ ϋ« * 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 297公釐） 552318ft clothing -------- II ------ 、 —— line 丨 Qin (please read the precautions on the back before filling this page) ϋ ϋ «* This paper size applies to China National Standard (CNS) A4 specification (21〇297 mm) 552318

五、發明說明（） (1)實驗材料將JISA3004合金鋁板進行DI加工後之未經洗淨之容器（66mm0x124mmh)。 (2 )實驗條件於各實施例、及各比較例中，已將液體溫度、處理方法及時間予以標示出了。然而，關於各洗淨工程，各實施例、及比較例皆依照下述之工程（1)〜（3 )。工程（1):標準處理 1.脫脂 2·水洗（20秒喷霧） 3·合成處理（20秒喷霧）藥劑：AROJIN N405 (日本PARKERIZING股份有限公司製）溫度：40°C " pH ： 2. 7 4·水洗（20秒喷霧） 5·去離子水洗（20秒喷霧） 6·乾燥（ 200°C 2分鐘）工程（2):滯留處理經濟部智慧財產局員工消費合作社印製 1.脫脂 2·滯留（脫脂空氣 3分鐘） 3·水洗（20秒喷霧） 1合成處理（20秒喷霧）公司製）V. Explanation of the invention () (1) Experimental materials Unwashed container (66mm0x124mmh) after DI processing of JISA3004 alloy aluminum plate. (2) Experimental conditions In each example and each comparative example, the liquid temperature, processing method and time have been marked. However, regarding each cleaning process, each of the examples and comparative examples follows the following processes (1) to (3). Process (1): Standard treatment 1. Degreasing 2. Washing (20 seconds spray) 3. Synthesis treatment (20 seconds spray) Medicament: AROJIN N405 (manufactured by PARKERIZING Co., Ltd.) Temperature: 40 ° C " pH: 2. 7 4 · Washing (20 seconds spray) 5 · Deionized water wash (20 seconds spray) 6 · Drying (200 ° C 2 minutes) Engineering (2): Retention processing Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 1. Degreasing 2. Retention (3 minutes of degreasing air) 3. Washing (20 seconds spray) 1 Synthetic treatment (20 seconds spray)

藥劑：AROJIN N405 (日本PARKERIZING股份有限溫度：40°C 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 552318Medicament: AROJIN N405 (Japan PARKERIZING Co., Ltd. Limited temperature: 40 ° C) This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) 552318

五、發明說明（） pH : 2. 7 5·水洗（20秒喷霧） 6·去離子水洗（20秒喷霧） 7·乾燥（ 200°C 2分鐘）工程（3):未處理 1.脫脂 2·水洗（20秒喷霧） 3·去離子水洗（20秒喷霧） 4·乾燥（ 200°C 2分鐘） (4 )確效實驗方法去污性：自卫程⑴、卫程（3)之乾燥後容器内側面，以同一透明膠帶（NICHIMN公司製），將三處地方以膠帶剝離，再將該膠帶貼附於白紙之上，並使用比色測定裝置（color computer) (SUGA實驗機製SM_3)進行五處地方之測定。亮度高（優）〇一 △一 X (劣）亮度低沾水性·工程（3)之去離子水洗之後，將容器放置30秒，對當時之沾水面積以百分比評定。經濟部智慧財產局員工消費合作社印製變黑性：於工程（η之後，將容器底部浸泡於沸騰自來水内30分鐘，將當時之黑色度以目測進行評定。無、交黑（優）1Q分<—···—> 1分（劣）變黑塗料密合度：於工程（丨）之後，塗抹環氧尿素系，以215 C鑛3分鐘（膜厚)，其後，將容器内面放入碁盤目，浸泡於下述實驗液之沸騰液中6〇分鐘，於水洗並V. Description of the invention () pH: 2. 7 5 · Washing (20 seconds spray) 6 · Deionized water wash (20 seconds spray) 7 · Drying (200 ° C 2 minutes) Engineering (3): Untreated 1. Degreasing 2. Washing with water (20 seconds spray) 3. Deionized washing with water (20 seconds spray) 4. Drying (200 ° C for 2 minutes) (4) Validation Test Method Detergency: Self-defense Cheng Wei, Wei Cheng (3 ), The inside surface of the container was dried with the same scotch tape (manufactured by NICHIMN Co., Ltd.), and the three places were peeled off with tape, and the tape was affixed to a white paper, and a color computer (SUGA test Mechanism SM_3) Performs measurements in five places. High brightness (excellent) 〇 △ △ X (poor) low brightness Water-washing · Engineering (3) After deionized water washing, place the container for 30 seconds, and evaluate the wetted area at that time as a percentage. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Co-operative Blackening: After the project (η, immerse the bottom of the container in boiling tap water for 30 minutes, and evaluate the blackness at that time by visual inspection. None, black (excellent) 1Q points < — ··· — > 1 point (inferiority) Black coating adhesion: After the process (丨), apply epoxy urea system for 215 C for 3 minutes (film thickness), and then, the inner surface of the container Put it into the paniculata, immerse it in the boiling solution of the following experimental solution for 60 minutes, wash in water and

552318 Λ7 B7 五、發明說明（自風乾後’進行膝帶之制離步驟，以目測進行評定。無，離（優）10分…· —1分（劣）有剝離二上述之貫驗液係為將於去離子水内加入氯化鈉5g/ L 板S夂5g/L加以溶解所得之溶液。 π滘外觀·於工程（2)後，以目測對底部之處理斑外觀進行評定。無處理斑（優）〇~△一 X (劣）有處理斑耐蝕性··於工程（3)之後，將容器底部浸泡於沸騰自來水内3分鐘，將當時之茶色度以目測進行評定。未變茶色（優）〇一△一X (劣）已變茶色實施例1 使用下述之洗淨液（1 )，於下述處理條件下進行處王里洗淨液（1) 氫氧化鉀 1. 0 g/L 碳酸鉀 5· 0 g/L 羥烷基二膦酸 l 0 g/L 庚葡糖酸鈉 2· 5 g/L 表面活性劑 2· 0 g/L 偏釩酸鈉（以V表示）〇· 05 g/乙 11.552318 Λ7 B7 V. Description of the invention (After the air-drying, the step of removing the knee strap is evaluated by visual inspection. No, 10 points away (excellent) ... 1 point (inferior) There is peeling.) This is a solution obtained by dissolving sodium chloride 5g / L plate S / 5g / L in deionized water and dissolving it. Π 滘 Appearance · After the project (2), visually evaluate the appearance of the treated spot on the bottom. No treatment Spot (excellent) 〇 ~ △ 一 X (poor) There is processing spot corrosion resistance. After the process (3), the bottom of the container is immersed in boiling tap water for 3 minutes, and the tea color at that time is evaluated visually. (Excellent) 〇 △△ X (Inferior) has been browned Example 1 Using the following cleaning solution (1), under the following processing conditions, Chu Wangli cleaning solution (1) potassium hydroxide 1.0 g / L potassium carbonate 5.0 g / L hydroxyalkyldiphosphonic acid 10 g / L sodium heptagluconate 2.5 g / L surfactant 2.0 g / L sodium metavanadate (expressed as V ) 05 g / B 11.

pH 處理條件溫度：50T：方法：喷霧時間：50秒 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) 552318pH processing conditions Temperature: 50T: Method: Spraying time: 50 seconds 10 This paper size applies to China National Standard (CNS) A4 (210 X 297 male f) 552318

經濟部智慧財產局員工消費合作社印製五、發明說明（）實施例2 使用下述之洗淨液（2)’於下述處理條件下進行處理。洗淨液（2) 氫氧化鉀碳酸鉀羥烷基二膦酸表面活性劑偏釩酸鈉（以V表示） pH 處理條件溫度：50°C 方法：浸泡時間：50秒實施例3 使用下述之洗淨液（3)，於下述處理條件下進行處洗淨液（3) 氫氧化鉀碳酸鉀羥烧基二膦酸庚葡糖酸鈉表面活性劑偏飢酸納（以V表不） ___π 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1.0 g/L 5.0 g/L 1. 〇 g/L 4· 0 g/L 〇. 05 g/L11.0Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention () Example 2 The following cleaning solution (2) 'was used for processing under the following processing conditions. Washing liquid (2) Potassium hydroxide, potassium carbonate, hydroxyalkyl diphosphonic acid surfactant, sodium metavanadate (indicated by V) pH Treatment condition temperature: 50 ° C Method: Soaking time: 50 seconds Example 3 The following is used The cleaning solution (3) was subjected to the following treatment conditions. (3) Potassium hydroxide, potassium carbonate, hydroxyalkyl diphosphonate, sodium hepterogluconate surfactant, sodium metaquinone (represented by V) ) ___ π This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 1.0 g / L 5.0 g / L 1. 〇g / L 4.0 · g / L 〇 05 g / L11.0

I 0 g/L 5·〇 g/L I 0 g/L 2· 5g/L 7· 5 g/L 0·05 g/LI 0 g / L 5.0 g / L I 0 g / L 2.5 g / L 7.5 g / L 0.5 g / L

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五、發明說明（） pH 處理條件溫度：60°C 方法：喷霧時間：40秒實施例4 使用下述之洗淨液（4)，於下述處理條件下進行處理洗淨液（4) 氫氧化鉀 11. 請先閱讀背意事項再V. Explanation of the invention () pH treatment condition temperature: 60 ° C Method: spraying time: 40 seconds Example 4 The following cleaning solution (4) was used, and the cleaning solution (4) was processed under the following processing conditions Potassium hydroxide 11. Please read the precautions before

填應1 頁I 經濟部智慧財產局員工消費合作社印製碳酸鉀羥烷基二膦酸庚葡糖酸鈉表面活性劑偏釩酸鈉（以V表示） pH 處理條件溫度：60°C 方法：喷霧時間：30秒實施例5 使用下述之洗淨液（5) 洗淨液（5) 氫氧化鉀碳酸鉀 1.0 g/L 2. 0 g/L 1. 〇 g/L 2. 5 g/L 4.0 g/L 0.05 g/L 9. 5 ;下述處理條件下進行處理 1· 4.Fill in 1 page I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, potassium carbonate, hydroxyalkyl diphosphonate, sodium hepterogluconate surfactant, sodium metavanadate (indicated by V) pH Treatment temperature: 60 ° C Method: Spray time: 30 seconds Example 5 The following cleaning solution (5) was used: Washing solution (5) Potassium hydroxide potassium carbonate 1.0 g / L 2. 0 g / L 1. 〇g / L 2. 5 g / L 4.0 g / L 0.05 g / L 9. 5; treatment under the following processing conditions 1 · 4.

g/L g/L 訂g / L g / L order

r Iit I 12 本紙張尺度適用中國國家標準（CNS)A4規格(210 x 297公$〜 552318 Λ7 五、發明說明（羥烷基二膦酸庚葡糖酸鈉表面活性劑偏釩酸鈉（以V表示 pH 處理條件溫度：50°C 方法：浸泡時間：50秒實施例使用下述之洗淨液（6 )，於下述處理條件下進行處理洗淨液（6) 氫氧化鉀經烧基二膦酸葡糖酸鈉表面活性劑氧釩乙醯醋酸鹽（以V表示 pH 處理條件溫度：70°C 方法：噴霧時間：5秒比較例1 3· 〇 g/L I 〇 g/L 2.5 g/L4· 〇 g/L 〇. 05 g/L 12.0 使用下述之洗淨液（7)，於下述處理條件下進a 13 訂線本纸張尺度適用中國國家標準(CNS)A4規格（21〇 X / 552318 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（）洗淨液（7) 氫氧化鉀 3. 0 g/L 庚葡糖酸鈉 2.5 g/L 表面活性劑 0 · 5 g/ L 偏釩酸鈉（以V表示） 0· 05 g/L pH 8. 5 處理條件溫度：50°C 方法：喷霧時間：30秒比較{列2 使用下述之洗淨液（8)，於下述處理條件下進行處理。洗淨液（8) 氫氧化鉀 1· 0 g/L 碳酸鉀 5. G g/L 羥烷基二膦酸 1. 0 g/L 庚葡糖酸鈉 2. 5 g/L 表面活性劑 4· 0 g/ L 偏叙酸鈉（以V表示） 0· 005 g/L pH 11.〇處理條件溫度：50°C 方法：喷霧時間：40秒本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -njl衣--------訂------‘—線丨1 552318 經濟部智慧財產局員工消費合作社印製五、發明說明（比較例理使用下述之洗淨液（9)，於下什老下述處理條件下進行處洗淨液（9) 氫氧化鉀碳酸鉀羥烷基二膦酸庚葡糖酸鈉表面活性劑硫酸鈽（以Ce表示）pH 處理條件溫度：50°C 方法：喷霧時間：50秒比較例4 使用下述之洗淨液（10)，於下述處理條件下進行處 I 0 g/L 5· 0 g/L l 0 g/L 2.5 g/L 4· 〇 g/L 0. 1 g/L 11· 5 理洗淨液（10) 氫氧化鉀 1 0 g/L 碳酸鉀 5· 〇 g/L 羥烧基二膦酸 L 0 g/L 庚葡糖酸鈉 2· 5 g/L 表面活性劑 4· ◦ g/L 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐）r Iit I 12 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 US $ ~ 552318 Λ7) V. Description of the invention (Hydroxyalkyl diphosphonate sodium heptagluconate surfactant sodium metavanadate (with V represents pH. Treatment temperature: 50 ° C. Method: Soaking time: 50 seconds. The following cleaning solution (6) is used in the example. The cleaning solution (6) is treated under the following processing conditions. Bisphosphonate sodium gluconate surfactant vanadylacetamidine acetate (represented by pH pH treatment conditions temperature: 70 ° C method: spraying time: 5 seconds Comparative Example 1 3 · 〇g / LI 〇g / L 2.5 g / L4 · 〇g / L 〇. 05 g / L 12.0 Use the following cleaning solution (7), and enter it under the following processing conditions. 13 Alignment This paper size applies the Chinese National Standard (CNS) A4 specification ( 21〇X / 552318 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Cleaning solution (7) Potassium hydroxide 3.0 g / L sodium heptoglucate 2.5 g / L surfactant 0 · 5 g / L sodium metavanadate (expressed as V) 0 · 05 g / L pH 8. 5 Processing conditions Temperature: 50 ° C Method: Spray time: 30 seconds Use the following cleaning solution (8) than {Column 2 and treat under the following processing conditions. Cleaning solution (8) Potassium hydroxide 1.0 g / L Potassium carbonate 5. G g / L hydroxyalkyl Diphosphonic acid 1.0 g / L sodium heptagluconate 2.5 g / L Surfactant 4.0 g / L Sodium metaxylate (expressed as V) 0 · 005 g / L pH 11.〇 Treatment conditions Temperature: 50 ° C Method: Spray time: 40 seconds This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -njl 衣- ------ Order ------'-- line 丨 1 552318 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (Comparative example uses the following cleaning solution (9), below The cleaning solution is carried out under the following treatment conditions: (9) Potassium hydroxide, potassium carbonate, hydroxyalkyl diphosphonate, sodium heptoglucate surfactant, osmium sulfate (expressed as Ce), pH treatment conditions, temperature: 50 ° C, method : Spraying time: 50 seconds Comparative Example 4 Using the following cleaning solution (10), the processing was performed under the following processing conditions: I 0 g / L 5.0 g / L l 0 g / L 2.5 g / L 4 · 〇g / L 0.1 g / L 11 · 5 cleaning solution (1 0) Potassium hydroxide 10 g / L Potassium carbonate 5.0 g / L Hydroxyl bisphosphonic acid L 0 g / L Sodium hepterogluconate 2.5 G / L Surfactant 4 ◦ g / L 15 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

552318 五、發明說明（經濟部智慧財產局員工消費合作社印制衣 Λ7 B7 鉬硝銨（molybdenum)酸（以 Mo 表示）〇· 1 g/L PH 11.0 處理條件溫度：50°C 方法：喷霧時間：50秒比較例5 使用下述之洗淨液（11)，於下述處理條件下進行處理。洗淨液（11) 氫氧化鉀 1. 0 g/L 碳酸鉀 5. 0 g/L 羥烷基二膦酸 1. 〇 g/L 庚葡糖酸鈉 2.5 g/L 表面活性劑 4. 0 g/L 鎢酸鈉（以W表示） 0. 1 g/L pH 11. 0 處理條件溫度：50T：方法：喷霧時間：50秒比較例6 使用下述之洗淨液（12)，於下述處理條件下進行處理。552318 V. Description of invention (Printed clothing Λ7 B7 Molybdenum acid (expressed as Mo) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 · 1 g / L PH 11.0 Processing condition temperature: 50 ° C Method: spray Time: 50 seconds Comparative Example 5 The following cleaning solution (11) was used, and the treatment was performed under the following processing conditions: Washing solution (11) potassium hydroxide 1.0 g / L potassium carbonate 5.0 g / L Hydroxyalkyldiphosphonic acid 1.0 g / L sodium heptoglucate 2.5 g / L surfactant 4.0 g / L sodium tungstate (represented by W) 0.1 g / L pH 11. 0 Processing conditions Temperature: 50T: Method: Spray time: 50 seconds Comparative Example 6 The following cleaning solution (12) was used, and the treatment was performed under the following processing conditions.

552318 A7 B7 五、發明說明（洗淨液（1 2 )552318 A7 B7 V. Description of the invention (Cleaning solution (1 2)

氫氧化鉀 1. 〇 g/LPotassium hydroxide 1. 〇 g / L

碳酸鉀 5. 0 g/LPotassium carbonate 5. 0 g / L

羥烷基二膦酸 1· G g/LHydroxyalkyl diphosphonic acid 1 G g / L

庚葡糖酸鈉 2.5 g/LSodium heptoglucate 2.5 g / L

表面活性劑 4· 0 g/L pH 11. 〇處理條件溫度：50°C 方法：喷霧時間：50秒上述實施例1〜6及比較例1〜6之評定結果將表示於表 1中請先閱讀背 & 意事項再Surfactant 4.0 · g / L pH 11. 〇 Treatment conditions Temperature: 50 ° C Method: Spray time: 50 seconds The evaluation results of the above Examples 1 to 6 and Comparative Examples 1 to 6 are shown in Table 1. Read & Matters Before Reading

填赢· 頁 I I I 訂Fill in and win · Page I I I Order

l·i I 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） __一本經濟部智慧財產局員工消費合作社印製 552318 五、發明說明（【表1】l · i I Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) __A printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 552318 5. Invention Description ([Table 1]

由表1所顯示之結果，可清楚地看出實施例1〜6所記錄之本發明之鹼性洗淨劑其去污力、沾水性、變黑性、塗料密合度、滯留外觀、耐蝕性等皆相當優異。另一方面， pH值低之比較例1中，其去污力、沾水性、變黑性、耐蝕性較為低劣。又，釩濃度低之比較例2中，則以滯留外觀、耐錄較為低劣。X，添加鈒料之金屬作為添加劑之比較例3〜5中，則以滯留外觀、耐蝕性較為低劣。又，於未含鈒化合物之比較例6中，則以變黑性、滞留外觀、耐姓性較為低劣。 --------訂-------—1^ (請先閱讀背面之；fd意事項再填寫本頁) 18 552318 Λ7From the results shown in Table 1, it can be clearly seen that the alkaline detergent of the present invention recorded in Examples 1 to 6 has detergency, water-tightness, blackening property, paint adhesion, retention appearance, and corrosion resistance. Etc. are all excellent. On the other hand, in Comparative Example 1 having a low pH, the detergency, water-staining, blackening, and corrosion resistance were inferior. In Comparative Example 2 where the vanadium concentration was low, the appearance of retention and the recording resistance were inferior. X. In Comparative Examples 3 to 5 in which an additive metal was added as an additive, the appearance of retention and the corrosion resistance were inferior. Moreover, in Comparative Example 6 which did not contain a fluorene compound, it was inferior in blackening property, retention appearance, and surname resistance. -------- Order -------— 1 ^ (Please read the back first; fill in this page with fd notes) 18 552318 Λ7

(以上各搁由本局填註 A4 年汇4曰 Φ'ά 552318 雲|專利説明書中文發明新型名稱英文鋁或鋁台金用洗淨液及洗淨方法(The above contents are filled out by the Bureau. A4 Annual Meeting 4 Φ'ά 552318 Cloud | Patent Specification Chinese Invention New Type Name English English Aluminum and Aluminum Alloy Gold Detergent and Method

CLEANING AGENTS AND METHODS FUR ALUMINUM OR ALUMINUM ALLOY 姓名⑴日野 (2廠野 (3)田中哉朗也和恭和國籍均曰本裝發明創作人住、居所 msisiiis 説· 訂姓名 (名稱）日本巴卡萊近沽股份有限公司經濟部智慧財產钧員工消費合作社印製國籍住、居所 (事務所）代表人姓名日本日本國東京都中央區日本橋卜15- 里昆菊雄本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 552318 歡 A7 B7 年月 91 11 五、發明說明（） L以上釩原子之釩化合物爲其特徵之鋁或鋁合金用洗淨液。又，本發明之上述鋁合金洗淨液之組成成分係含有自鹼金屬氫氧化物、無機磷酸鹼金屬鹽及碳酸鹼金屬鹽中所選出，至少含有一種以上之鹼性組份0.5〜50.Og/L、爲釩原子狀態之釩化合物0.01〜10.〇g/L、及表面活性劑 0.01〜10.0g/L，爲具PH9.0〜13.0之鋁或鋁合金用鹼性洗淨液。更進一步，本發明爲一種鋁或鋁合金之鹼性洗淨方法，將上述鹼性洗淨液加熱至30〜80t，以噴霧法或浸泡法與鋁或鋁合金表面接觸2秒以上爲其特徵。【發明之實施形態】本發明係爲一種鹼性洗淨液，關於一種以含有爲釩原子狀態之釩化合物〇.〇lg/L爲其特徵之鋁或鋁合金用洗淨液。特別以含有自鹼金屬氫氧化物、無機磷酸鼓金屬鹽及碳酸鹼金屬鹽中所選出，至少含有一種以上鹼性組份〇.〇5〜50.0g/L 、爲釩原子狀態之釩化合物0.01〜10.〇g/L、及表面活性劑 0.01〜10.0g/L，爲具pH9.0〜13.0之鋁或鋁合金用鹼性洗淨液爲其理想。作爲本發明之鹼性洗淨液之鹼性成分所使用之鹼金屬鹽，係爲鉀或鈉之氫氧化物、碳酸鹽及無機磷酸鹽；例如，氫氧化鈉、碳酸鈉、二代磷酸鈉、氫氧化鉀、碳酸鉀等，至少含有以上所述之一種以上。含有量係爲0.5〜50.0g/L，理想則爲1.0〜10.〇g/L。若未達到0.5g/L，則會由於蝕刻不足，於鋁或鋁合金表面產生不均勻之現象。又，反之，若超過50.0g/L，則就鈾刻面及性能面上來CLEANING AGENTS AND METHODS FUR ALUMINUM OR ALUMINUM ALLOY Co., Ltd. Intellectual Property of the Ministry of Economic Affairs of the People's Republic of Japan Consumer Co-operative Printing Nationality Residence, Residence (Office) Representative Name Japan Nihonbashi, Chuo-ku, Tokyo, Japan 15- Rikun Kikuo This paper is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 552318 Huan A7 B7 January 91 11 V. Description of the invention () A vanadium compound with vanadium atoms above L is characterized by a cleaning solution for aluminum or aluminum alloy. In addition, the above-mentioned aluminum alloy cleaning solution of the present invention The composition is a vanadium compound selected from the group consisting of alkali metal hydroxides, inorganic phosphate alkali metal salts and carbonate alkali metal salts, and contains at least one basic component of 0.5 to 50.Og / L in the state of vanadium atom. 0.01 to 10.0.0 g / L and surfactant 0.01 to 10.0 g / L are alkaline cleaning solutions for aluminum or aluminum alloys having a pH of 9.0 to 13.0. Furthermore, the hair It is an alkaline cleaning method of aluminum or aluminum alloy. The above-mentioned alkaline cleaning solution is heated to 30 ~ 80t, and it is characterized by contacting the surface of aluminum or aluminum alloy with spray method or immersion method for more than 2 seconds. [Form] The present invention is an alkaline cleaning solution, and relates to a cleaning solution for aluminum or aluminum alloy, which is characterized by containing a vanadium compound in the state of vanadium atom, lg / L. Especially, it contains self-alkali metal hydrogen It is selected from oxides, inorganic phosphoric acid drum metal salts and alkali metal carbonate salts, and contains at least one basic component of 0.05 to 50.0 g / L, and a vanadium compound in a vanadium atom state of 0.01 to 10.0.0 g / L. And surfactant 0.01 ~ 10.0g / L, it is ideal to use alkaline cleaning solution for aluminum or aluminum alloy with pH 9.0 ~ 13.0. It is used as the alkaline component of the alkaline cleaning solution of the present invention. Alkali metal salts are hydroxides, carbonates, and inorganic phosphates of potassium or sodium; for example, sodium hydroxide, sodium carbonate, sodium diphosphate, potassium hydroxide, potassium carbonate, etc., containing at least one of the above The content is above 0.5 ~ 50.0g / L, ideally 1.0 ~ 10.〇g / L. If it does not reach 0.5 g / L, it will cause unevenness on the surface of aluminum or aluminum alloy due to insufficient etching. On the other hand, if it exceeds 50.0 g / L, the uranium facet and performance surface will come.

S 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝--------訂----------線i 經濟部智慧財產局員工消費合作社印製 552318 A7 B7S This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page). -------- Order ------- --- Line i Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 552318 A7 B7

BLL 月經濟部智慧財產局員工消費合作社印製五、發明說明（）看，也未能產生更好的效果，且鋁表面會因過度鈾刻而變得粗糙，並非理想狀態。作爲釩化合物，含有可得價電子釩之無機或有機化合物皆適用。例如，偏釩酸、釩酸、及此類之鹽類（例如：鈉、鉀、銨等）、五氧化釩等氧化釩；五氯化釩或五氟化釩等鹵化釩；氧釩基硫酸、硫酸釩、硝酸釩、磷酸釩、重磷酸釩、醋酸釩等釩鹽；及釩乙醯醋酸鹽、氧釩乙醯醋酸鹽等有機釩化合物等。上述含有銳原子0.01〜10.0g/L，理想則爲含有0·05〜5.0g/L。未達到0.01g/L時，並無法針對乾燥時之變色問題及滯留罐之外觀達到效果；反之，若含超過0.5g/L·之釩原子量亦無法針對改善乾燥時之變色及滯留所造成之罐外觀不良等問題達到效果；反之，若釩原子含量超過0.5 g/L時亦無法達到所希望效果，且會導致成本增加，亦並不理想。表面活性劑係並未特別限定爲陽離子型表面活性劑、陰離子型表面活性劑、亦或非離子表面活性劑；例如，非離子型爲碳氫化合物衍生物（derivative)、松香亭酸（abietinic acid)衍生物、第一級乙氧基（ethoxy)化乙醇、變性聚乙氧基（polyethoxy)化乙醇，至少含有以上所述之任一種以上。表面活性劑係含有0.01〜10.〇g/L。又，處理液內，由於混入被處理金屬內所溶出之金屬離子，可能產生沉澱之情形。遇此情況，可於處理液內添加金屬離子封鎖劑。所謂的金屬離子封鎖劑，係例如氨烷基膦酸 (amino alkyl phosphonic acid)、經院基二膦酸 (diphosponate)等。除此之外，葡糖酸（gluconic acid) 鹼金屬鹽、庚葡糖酸（heptagluconic)鹼金屬鹽、草酸鹼 ^ 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）丨·裝--------訂----------線---- (請先閱讀背面之注咅？事項再填寫本頁)BLL printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () It also failed to produce a better effect, and the aluminum surface would become rough due to excessive uranium etching, which is not ideal. As the vanadium compound, inorganic or organic compounds containing available valence electron vanadium are suitable. For example, metavanadic acid, vanadic acid, and such salts (for example: sodium, potassium, ammonium, etc.), vanadium oxide such as vanadium pentoxide; vanadium halide such as vanadium pentachloride or vanadium pentafluoride; vanadyl sulfate , Vanadium salts such as vanadium sulfate, vanadium nitrate, vanadium phosphate, vanadium double phosphate, vanadium acetate; and organic vanadium compounds such as vanadium acetoacetate, vanadyl acetate and the like. The foregoing contains 0.01 to 10.0 g / L of sharp atoms, and preferably contains 0.05 to 5.0 g / L. If it does not reach 0.01g / L, it will not be able to achieve the effect of discoloration during drying and the appearance of the retention tank; conversely, if it contains vanadium atomic weight exceeding 0.5g / L ·, it will not be able to improve the discoloration and retention caused by drying. Problems such as poor appearance of the tank achieve the effect; on the contrary, if the vanadium atom content exceeds 0.5 g / L, the desired effect cannot be achieved, and the cost will increase, which is also not ideal. The surfactant system is not particularly limited to a cationic surfactant, an anionic surfactant, or a nonionic surfactant; for example, the nonionic is a hydrocarbon derivative (derivative) or abietinic acid ) Derivatives, primary ethoxylated ethanol, and denatured polyethoxylated ethanol, containing at least any one or more of the above. The surfactant system contains 0.01 to 10.0 g / L. In addition, metal ions dissolved in the treated metal may be mixed into the processing solution, which may cause precipitation. In this case, a metal ion blocking agent can be added to the treatment solution. The so-called metal ion blocking agents are, for example, amino alkyl phosphonic acid, diphosponate, and the like. In addition, gluconic acid alkali metal salt, heptagluconic alkali metal salt, oxalate alkali ^ 6 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) 丨 installed -------- order ---------- line ---- (Please read the note on the back? Matters before filling this page)

Claims

552318 A8 B8 年月 β 六、申請專利範圍 1. 一種鋁或鋁合金用鹼性洗淨液，其組成特徵爲含有至少一種選自鹼金屬氫氧化物、無機磷酸鹼金屬鹽及碳酸鹼金屬鹽之鹼性組份（builder) 0.5-50.0克/升、爲釩原子狀態之釩化合物0.0M0克/升、表面活性劑 0.1-10.0克/升、及金屬離宇封鎖劑0.1-10.0克/升，且其具有pH 9.0-13.0之酸鹼値。 2. 一種鋁或鋁合金用之鹼性洗淨方法，其特徵爲將如申請專利範圍第1項所述之鹼性洗淨液予以加熱至30-80 °C，使用噴霧法或浸泡法使鋁或鋁合金表面與其接觸 2秒以上。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）552318 A8 B8 in the year of June β 6. Application for patent scope 1. An alkaline cleaning solution for aluminum or aluminum alloy, the composition is characterized by containing at least one selected from the group consisting of alkali metal hydroxide, inorganic phosphate alkali metal salt and alkali metal carbonate The basic component (builder) is 0.5-50.0 g / l, the vanadium compound in the state of vanadium atom is 0.0M0 g / l, the surfactant is 0.1-10.0 g / l, and the metal blocking agent 0.1-10.0 g / l And it has a pH value of 9.0-13.0. 2. An alkaline cleaning method for aluminum or aluminum alloy, characterized in that the alkaline cleaning solution as described in item 1 of the scope of patent application is heated to 30-80 ° C, and is sprayed or immersed The surface of aluminum or aluminum alloy is in contact with it for more than 2 seconds. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm)