1232237 玖、發明說明： 發明所屬之枝術領域 本發明係關於氨基磺酸-羥基羧酸系洗潔劑，特別，在 淸洗附著鈣化合物之金屬製品時，可防止金屬之氫脆性及 金屬溶出之同時，可發揮優良洗潔性能的氨基磺酸-羥基 羧酸系之金屬製品用淸潔劑。 先前技術 由食物剩渣之分解所產生之水不溶性有機物附著於廚 房之排水管的內壁，尿等之污染物所分解產生之鈣化合物 附著於馬桶之排水管的內壁所發生之排水管堵塞問題。 使此等排水管內之附著物（一般稱爲積垢（Scale))加以 去除具有高效果之藥品係有塩酸或硫酸等之強酸性無機酸 等，使用此等藥品時連同腐鈾形成排水管之材料。又，淸 洗後之排水也會引起環境污染之問題。_ 一方面，雖有卸下排水管以物理方法進行去除積垢， 此種淸潔作業，爲不舒適且爲困難之作業，特別，使配裝 於狹窄空間內之複雜配管加以分解淸洗之作業係爲需長時 間的作業。 於是，爲解除使用上述之強酸性藥品時的問題點之同 時，積垢淸潔能力高的氨基磺酸-羥基羧酸系淸潔劑受注 目。例如，在日本專利公開特許公報2000-63890號係記 述以含如蘋果酸、檸檬酸之羥基羧酸化合物的至少一種以 上與，氨基磺酸之至少一種以上的組成物所構成之一種去 除劑。此種淸潔劑係可有效去除如不使用習知之無機酸、 11298pif.doc/008 5 1232237 無機碱無法加以去除的石灰質化之齒石，排水管壁所附著 之積垢等的同時，爲容易處理及不污染環境之淸潔劑具有 可安全加以使用之長處。 一方面，日本專利特開2000-64096號係對含有氨基磺 酸及羥基羧酸爲必須成分之積垢去除劑加以記述，對羥基 羧酸係例如以使用乙醇酸（glycollic acid)或蘋果酸爲宜。 又，對配合比率（重量比）係以氨基磺酸··羥基羧酸在5 : %〜30: 70爲宜。此去除劑，對附著於滲析機器等之積垢（主 要爲碳酸鈣）之溶解力高，又，比習知之酸淸潔劑有金屬 腐蝕少之長處。又，此去除劑係無臭，對人體及環境之安 全性高。 如此，氨基磺酸-羥基羧酸系淸潔劑係對附著鈣化合物 之淸潔對象物之淸洗有效，多數酸，不管有機、無機，與 金屬接觸時會產生氫氣。此氫氣吸藏於金屬中，原子狀氫 蓄積於晶界（gain boundary)，集積在空孔時發生金屬裂開 之破壞。即，成爲金屬之氫脆性的原因。一方面，氨基磺 酸係所知爲具有強力引起金屬離子之溶出的性質。上述之 淸潔劑或去除劑雖係優於積垢之去除性能的同時，有不危 及人體及環境之長處，從一面由淸潔對象物低減金屬溶出 量，一面防止淸潔對象物之氫脆性的觀點依然尙有改善之 餘地。特別，在日本專利特開2000-64069號所記述之去 除劑，係以羥基羧酸之量比氨基磺酸之量較多之關係’由 淸潔對象物之材質氫脆性有可能變成爲深刻問題之虞。 發明內容 11298pif.doc/008 6 1232237 因此，本發明之主要目的係提供一種氨基磺酸_羥基羧 酸系淸潔劑’在使附著鈣化合物等之如金屬製品的被淸潔 物加以淸洗時，具有可一面以高淸洗力，一面能抑止金屬 之氫脆性及金屬溶出之優良能力。 即，本發明之淸潔劑係包含氨基磺酸、及羥基羧酸之 至少一種的淸潔劑，氨基磺酸：羥基羧酸之至少一種的配 合比率爲50〜98:50:2,較好爲60〜95:40〜5,更好係80〜95 : 20〜5。 特別，對羥基羧酸，使用檸檬酸與蘋果酸，使氨基磺 酸：檸棋酸：蘋果酸之配合比率爲80〜95 : 10〜2.5 : 10〜2.5 之場合，係可得優良淸潔性能之同時，能發揮抑止氫脆性 及金屬溶出之最高性能。 本發明之更詳細特徵及其所有的效果，係可依據以下 詳述之實施發明的最佳形態能明確加以理解。 如以上所述，以包含氨基磺酸、及羥基羧酸之至少一 種，氨基磺酸：上述羥基羧酸之至少一種的配合組成（重 量比）爲50〜98 : 50〜2、較好爲60〜95 : 40〜5，更好係80〜95 : 20〜5爲特徵的本發明之氨基磺酸-羥基羧酸系淸潔劑，係 在淸潔力與，防止從淸潔對象物之金屬溶出再加上，對金 屬之氫脆性防止能力也可發揮優良性能。 在最重視提供安全性服務之航空、船舶及鐵路等業界， 在飛機、船體或車輛等之淸洗選定淸潔劑時特別加以重 視。另一方面，爲對應於繁密之運轉時程，需要縮短淸潔 或維護所需之時間，即，維持優良之淸洗力也成爲重要條 11298pif.doc/008 7 1232237 件以回應此種嚴格要求之淸潔劑係對趣基竣酸以使用 檸檬酸與蘋果酸，氨基磺酸：檸檬酸··蘋果酸之配合比率 爲80〜95 : 1〇〜2·5 : 10〜2.5，例如推荐使用實施例i或2 的淸潔劑。 ~ 本發明之氨基擴酸-經基羧酸系淸潔劑係不限於飛機、 船舶或鐵路車輛等，也可使用於氫脆性或金屬溶出成爲問 題的種種領域，爲不危及環境高淸潔能力之淸潔劑在產業 上具有高的利用價値。 爲議本發明之上述原理和其他目的、特徵和優點能更 明顯易懂，下文特舉一較佳實施例，並配合所附表格，作 詳細說明如下： 實施方式 在本發明之淸潔劑所使用之氨基擴酸係，例如，可使 用氨基擴酸（Sulfaminic acid)、氨基擴酸（amidosulfonic acid) 之N-烷基（alkyl)及N-烯丙基(allyl)衍生物等。 又，羥基羧酸係在其分子構造中包含乙醇（alchol)性羥 基(hydroxide radical)與，竣基（carboxyl)之總稱，例如，可 使用從蘋果酸檸檬酸、乙醇酸（glycolic acid)、乳酸（lactic cid)、酒石酸(tartaric acid)、經基丙酸(hydracrylic acid)、 α -經基丁酸（a -hydroxybutyric acid)、甘油酸（glyceric acid)、丙醇二酸（tartronic acid)、水楊酸（salicylic acid)、 間羥基苯甲酸（m-hydroxybenzoic acid)、對經基苯甲酸（p-hydroxybenzoic acid)、沒食子酸（gallic acid)、苯乙醇酸 (mandelic acid)、托品酸(tropaic acid)等選擇至少一'種，其 11298pif.doc/008 8 1232237 中，以使用蘋果酸及/或檸檬酸爲宜。 在本發明’係氨基磺酸與羥基羧酸之配合比率爲極重 要。即’氨基擴酸：淫基羧酸之配合之比率（重量比）爲 50〜98 : 50〜2、較好爲6〇〜95 : 4〇〜5、更好係8〇〜95 : 2〇〜5。 在羥基羧酸之配合比率爲5〇以上之場合，雖係可維持淸 洗力，對淸潔對象物之金屬有產生氫脆性之虞。又，在羥 基羧酸之配合比率爲2以下的場合，氨基磺酸-羥基羧酸 系淸潔劑之淸洗力低降之同時，由氨基磺酸之金屬離子溶 出量以顯著增大。 特別’對經基羧酸使用檸檬酸與蘋果酸時，以使氨基 磺酸：檸檬酸：蘋果酸之配合比率（重量比）在80〜95 : 10〜2·5 : 10〜2.5爲宜。又，此種場合，係使檸檬酸與蘋果 酸以等量爲宜。具體的係使氨基磺酸：檸檬酸··蘋果酸之 配合比率(重量比）在85 : 7.5 : 7.5、90 : 5 : 5或95 : 2.5 : 2.5爲宜。此等係如以下之實施例之結果所示，在本發明 之淸潔劑中’在淸潔力、淸潔對象物之氫脆性的防止，及 由淸潔對象物之金屬溶出的抑止等之各方面特別可提供優 良性能。 實施例 以下，依據實施例詳細說明本發明之氨基磺酸-羥基羧 酸系淸潔劑。 (實施例1〜7及比較例1〜5) (1)淸潔溶液之製作 使氨基磺酸、檸檬酸、蘋果酸依據第1表之配合組成 11298pif.doc/008 9 1232237 加以混合製作淸潔劑，在淸潔劑添加所定量之水以製作 10%水溶液。以此等作爲實施例1〜7及比較例1〜5之淸潔 溶液加以使用。 [第1表] (重量％) 氨基擴酸 檸檬酸 蘋果酸 實施例1 90 5 5 實施例2 85 7.5 7.5 實施例3 85 15 0 實施例4 85 0 15 實施例5 80 10 10 實施例6 70 15 15 實施例7 60 20 20 比較例1 100 0 0 比較例2 10 0 90 比較例3 20 40 40 比較例4 40 60 0 比較例5 0 100 0 (2)淸潔力 使以上所得的淸潔溶液500ml裝入燒杯，在此等燒杯 投入定量之碳酸鈣（固體）以緩慢一面加以攪拌（每分約30 回轉）一面加以測定每所定時間之碳酸鈣的溶解量。將結 果表示於第2表。 11298pif.doc/008 10 1232237 [第2表] 溶解量 從試驗開始之時間 (g) 5分 10分 15分 20分 實施例1 12 20 24 29 實施例2 11 18 20 22 實施例3 11 18 20 22 實施例4 11 18 20 22 實施例5 10 17 18 20 實施例6 10 17 18 20 實施例7 10 15 17 19 比較例1 15 25 30 40 比較例2 5 10 12 15 比較例3 5 10 12 15 比較例4 7 12 15 18 比較例5 3 7 9 10 (3)金屬溶出防止性能 茲爲評價由淸潔溶液對淸潔對象物之腐蝕性，加以測 定因淸洗而從淸潔對象物之鈦（Titanium)離子的溶出量。 淸潔對象物係使用具有15cm X 15cm X 6mm之形狀的鋼板 (JISSS41 : —般構造用壓延鋼板）。試驗溫度爲20°C。鈦 離子溶出量係從試驗開始在各經過1 hr、24hrs、48hrs、12Ohrs 之時間，以感應結合型等離子（plasma)發光分光分析法加 以測定。將其結果表示於第3表。 11298pif.doc/008 11 1232237 [第3表] 鈦離子溶出量 從試驗開始之時間 (β g/ml) lhr 24hrs 48hrs 120hrs 實施例1 <0.1 <0.1 <0.1 <0.1 實施例2 <0.1 <0.1 <0.1 <0.1 實施例3 <0.1 0.18 0.25 0.30 實施例4 <0.1 0.16 0.21 0.25 實施例5 <0.1 0Λ5 0.20 0.22 實施例6 <0.1 0.16 0.21 0.25 實施例7 <0.1 0.16 0.21 0.25 比較例1 <0.1 0.30 0.40 0.55 比較例2 <0.1 <0.1 <0.1 <0.1 比較例3 <0.1 <0.1 <0.1 0.10 比較例4 <0.1 <0.1 <0.1 0.15 比較例5 <0.1 <0.1 <0.1 <0.1 (4)氫脆性防止性能 茲爲評價由淸潔溶液對淸潔對象物之氫脆性，使鈦試 驗片浸漬於實施例1〜7及比較例1〜5之淸潔溶液一週後， 對試驗片進行以下之反復應力負載試驗以計測在試驗片發 生龜裂時之應力負載次數。試驗片係使用具有2mm(厚度）X 20mm(寬度）xl00mm(長度）尺寸之鈦金屬板。反復應力負 載試驗係使浸漬於淸潔溶液一週之鈦金屬板以一端固定成 爲懸臂梁式，以直徑l〇mm之圓棒爲按壓棒，按壓壓力約 爲2kg、衝程（stroke)寬爲2mm ’試驗溫度爲20°c ’按壓 11298pif.doc/008 12 1232237 頻度爲1次/秒之條件下在從鈦金屬板之他端約25mm附近 以反復的使鹰力加以負載。試驗係繼續至以目視認出在鈦 金屬板發生龜裂。到龜裂發生之所需應力負載次數愈少， 表75由氫J危性之鈦金屬板的材料劣化愈大。換言之，到龜 裂發生所需應力負載次數愈多時對淸潔溶液之氫脆性防止 能力爲高。. [第4表] 將試驗結果表示於第4表。 到龜裂發生時之應力負載次數 實施例1 3525 實施例2 3530 實施例3 3550 實施例4 3510 實施例5 3580 實施例6 2815 實施例7 2803 比較例1 3550 比較例2 1800 比較例3 1815 比較例4 2500 比較例5 1800 (5)結果 從以上之實驗結果，使用氨基磺酸100%之淸潔劑（比 較例1)之場合，雖可回避氫脆性問題，金屬（鈦）離子溶出 量極多不適於做爲淸潔劑。又，使用檸檬酸100%之淸潔 11298pif.doc/008 13 1232237 劑（比較例5)之場合，雖金屬溶出量變少，其淸潔力之低 降大的同時，容易產生氫脆性’不適合做爲本發明的目的 之金屬製品用淸潔劑。更且’對於以與本發明相異組成所 構成之比較例2〜4的氨基磺酸-羥基羧酸系淸潔劑’雖淸 潔力以某程度提高，且金屬溶出量少，但因氫脆性之關係 以少的應力負載次數就發生龜裂。此等結果表示以比較例 之配合組成無法提供具有①淸潔力、②金屬溶出量防止能 力③氫脆性防止能力的三個特性全部之優良清潔劑。 對此，實施例1〜7之結果係表示在本發明之組成範圍 可提供具有一面可維持高淸潔力一面能抑止氫脆性及金屬 溶出的優良能力之淸潔劑。持別’以實施例1及實施例2 之配合組成所製作的淸潔劑，藉由以其大部分（80%以上) 爲氨基磺酸，剩餘部分由等量之檸檬酸與蘋果酸加以構成 時，以得一面可維持使用氨基磺酸100%之淸潔劑的場合 之淸潔力的約70%或以上，關於金屬離子之溶出量低減至 1/5以下，更且關於氫脆性防止能力係與氨基磺酸1〇〇%之 淸潔劑同等之結果。 因此，在可維持氨基磺酸100%之淸潔劑所得的高淸潔 力與氫脆性防止能力，能克服氨基磺酸100%的淸潔劑的 最大缺點之低的金屬溶出防止性能上，特別以使用具有本 發明之實施例1或實施例2的配合組成之淸潔劑，即，氨 基磺酸：檸檬酸：蘋果酸之配合比率爲80〜95 : 10〜2.5 : 10〜2.5的淸潔劑爲宜。 雖然本發明已以一較佳實施例揭露如上，然其並非用 11298pif.doc/008 t 14 1232237 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍內，當可作些許之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 圖式之簡單說明 Μ j \\\ 圖式之標示說明·· Μ j \ \\ 11298pif.doc/008 151232237 发明 Description of the invention: Field of the invention to which the invention belongs The present invention relates to sulfamic acid-hydroxycarboxylic acid-based detergents. In particular, when washing metal products with calcium compounds attached, it can prevent hydrogen embrittlement of metals and metal elution. At the same time, a detergent for sulfamic acid-hydroxycarboxylic acid-based metal products that can exhibit excellent cleaning performance. In the prior art, water-insoluble organic matter produced by the decomposition of food residues adhered to the inner wall of the kitchen drain pipe, and calcium compounds produced by the decomposition of pollutants such as urine adhered to the inner wall of the toilet's drain pipe. problem. Removal of the attachments (commonly referred to as scale) in these drainage pipes. Highly effective medicines are strong acidic inorganic acids such as osmic acid or sulfuric acid. When using these medicines, they form a drainage pipe together with uranium decay. Of materials. In addition, the drainage after washing can cause environmental pollution. _ On the one hand, although there is a physical method to remove the dirt by removing the drain pipe, this cleaning operation is uncomfortable and difficult. In particular, the complicated pipes installed in a narrow space are decomposed and washed. Assignments are assignments that take a long time. Therefore, in order to solve the problems when using the above-mentioned strongly acidic medicines, sulfamic acid-hydroxycarboxylic acid-based detergents with high scale-cleaning ability have attracted attention. For example, Japanese Patent Laid-Open Publication No. 2000-63890 describes a removing agent composed of at least one or more hydroxycarboxylic acid compounds such as malic acid and citric acid and at least one or more types of sulfamic acid. This type of detergent can effectively remove calcified calculus, which cannot be removed without the use of conventional inorganic acids, 11298pif.doc / 008 5 1232237, and the scale attached to the drainage pipe wall. Cleaning agents that do not pollute the environment have the advantage of being safe to use. On the one hand, Japanese Patent Laid-Open No. 2000-64096 describes a scale removing agent containing sulfamic acid and hydroxycarboxylic acid as essential components. For hydroxycarboxylic acid, for example, glycolic acid or malic acid is used. should. The compounding ratio (weight ratio) is preferably 5:% to 30:70 for sulfamic acid · hydroxycarboxylic acid. This remover has high dissolving power to the scale (mainly calcium carbonate) attached to the dialysis machine, etc., and it has less metal corrosion than the conventional acid detergent. In addition, this remover is odorless and has high safety to human body and environment. In this way, sulfamic acid-hydroxycarboxylic acid detergents are effective for cleaning objects to which calcium compounds are adhered. Most acids, regardless of whether they are organic or inorganic, generate hydrogen when they come into contact with metals. This hydrogen is occluded in the metal, and atomic hydrogen accumulates in the gain boundary. When it accumulates in the pores, the metal cracks and breaks. That is, it causes hydrogen embrittlement of metals. On the one hand, sulfamic acid is known to have the property of causing strong dissolution of metal ions. Although the above-mentioned cleaning agents or removers are superior to the removal performance of scales, they have the advantages of not endangering the human body and the environment. On the one hand, the amount of metal eluted from the cleaning objects is reduced, and the hydrogen embrittlement of the cleaning objects is prevented. There is still little room for improvement. In particular, the removal agent described in Japanese Patent Laid-Open No. 2000-64069 is related to the fact that the amount of hydroxycarboxylic acid is larger than the amount of sulfamic acid. 'The material's hydrogen embrittlement may become a deep problem. Risk. SUMMARY OF THE INVENTION 11298pif.doc / 008 6 1232237 Therefore, the main object of the present invention is to provide a sulfamic acid-hydroxycarboxylic acid-based cleaning agent when washing a cleaning object such as a metal product to which a calcium compound and the like are attached. It has excellent ability to suppress the hydrogen embrittlement and metal dissolution of metals with high scouring power. That is, the detergent of the present invention is a detergent containing at least one of sulfamic acid and hydroxycarboxylic acid, and the compounding ratio of at least one of sulfamic acid: hydroxycarboxylic acid is 50 to 98: 50: 2, preferably It is 60 ~ 95: 40 ~ 5, more preferably 80 ~ 95: 20 ~ 5. In particular, for hydroxycarboxylic acids, citric acid and malic acid are used, and when the mixing ratio of sulfamic acid: citrate acid: malic acid is 80 to 95: 10 to 2.5: 10 to 2.5, excellent cleaning performance can be obtained. At the same time, it can exert the highest performance of suppressing hydrogen embrittlement and metal dissolution. The more detailed features of the present invention and all its effects can be clearly understood based on the best mode for carrying out the invention detailed below. As described above, the composition (weight ratio) of sulfamic acid: at least one of sulfamic acid and hydroxycarboxylic acid, and the content of at least one of hydroxycarboxylic acid is 50 ~ 98: 50 ~ 2, preferably 60 ~ 95: 40 ~ 5, more preferably 80 ~ 95: 20 ~ 5. The sulfamic acid-hydroxycarboxylic acid-based cleaning agent of the present invention is characterized by cleaning power and prevents metal from cleaning objects. In addition to dissolution, the ability to prevent hydrogen embrittlement of metals can also exert excellent performance. In the aviation, shipping, and railway industries that place the highest priority on providing safety services, special attention is paid to cleaning agents when cleaning aircraft, hulls, or vehicles. On the other hand, in order to correspond to the dense operation schedule, it is necessary to shorten the time required for cleaning or maintenance, that is, maintaining excellent cleaning power has also become important. 11298pif.doc / 008 7 1232237 pieces in response to such strict requirements Detergent is based on citric acid, using citric acid and malic acid, and sulfamic acid: citric acid. The ratio of malic acid is 80 ~ 95: 10 ~ 2 · 5: 10 ~ 2.5. For example, it is recommended to use Example i or 2 detergent. ~ The amino acid-acid-based carboxylic acid detergents of the present invention are not limited to airplanes, ships, or railway vehicles, but can also be used in various fields where hydrogen embrittlement or metal dissolution is a problem, and are not harmful to the environment. Detergents have a high price in the industry. In order to make the above principles and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below and described in detail with the accompanying table as follows: The embodiments are described in the detergents of the present invention As the amino acid used, for example, Sulfaminic acid, N-alkyl and N-allyl derivatives of amidosulfonic acid can be used. In addition, a hydroxycarboxylic acid system includes a general term of an alcoholic hydroxide radical and a carboxyl in its molecular structure. For example, malic citric acid, glycolic acid, and lactic acid can be used. (Lactic cid), tartaric acid, hydracrylic acid, α-a-hydroxybutyric acid, glyceric acid, tartronic acid, water Salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid, mandelic acid, tropic acid (tropaic acid) and the like are selected at least one kind, and among 11298pif.doc / 008 8 1232237, malic acid and / or citric acid is preferably used. In the present invention, the compounding ratio of the sulfamic acid to the hydroxycarboxylic acid is extremely important. That is, the ratio (weight ratio) of the compounding of amino acid and carboxylic acid is 50 ~ 98: 50 ~ 2, preferably 60 ~ 95: 40 ~ 5, more preferably 80 ~ 95: 2. ~ 5. When the mixing ratio of the hydroxycarboxylic acid is 50 or more, although the washing power can be maintained, hydrogen embrittlement may occur to the metal of the cleaning object. When the mixing ratio of the hydroxycarboxylic acid is 2 or less, the washing power of the sulfamic acid-hydroxycarboxylic acid-based detergent is lowered, and the amount of metal ions eluted from the sulfamic acid is significantly increased. In particular, when citric acid and malic acid are used for the transcarboxylic acid, the mixing ratio (weight ratio) of aminosulfonic acid: citric acid: malic acid is preferably 80 to 95:10 to 2.5: 10 to 2.5. In this case, it is preferable to use the same amount of citric acid and malic acid. Specifically, the mixing ratio (weight ratio) of sulfamic acid: citric acid · malic acid is preferably 85: 7.5: 7.5, 90: 5: 5, or 95: 2.5: 2.5. These are as shown in the results of the following examples. Among the cleaning agents of the present invention, the prevention of cleaning power, hydrogen embrittlement of cleaning objects, and the suppression of metal elution from cleaning objects, etc. All aspects can especially provide excellent performance. Examples Hereinafter, the sulfamic acid-hydroxycarboxylic acid-based detergent of the present invention will be described in detail based on examples. (Examples 1 to 7 and Comparative Examples 1 to 5) (1) Preparation of cleaning solution Aminosulfonic acid, citric acid, and malic acid were mixed according to the composition of Table 1 to 11298pif.doc / 008 9 1232237 to prepare cleaning solution. Agent, add a certain amount of water to the detergent to make a 10% aqueous solution. These were used as cleaning solutions of Examples 1 to 7 and Comparative Examples 1 to 5. [Table 1] (% by weight) Amino acid citrate malate Example 1 90 5 5 Example 2 85 7.5 7.5 Example 3 85 15 0 Example 4 85 0 15 Example 5 80 10 10 Example 6 70 15 15 Example 7 60 20 20 Comparative example 1 100 0 0 Comparative example 2 10 0 90 Comparative example 3 20 40 40 Comparative example 4 40 60 0 Comparative example 5 0 100 0 (2) Cleaning power 500 ml of the solution was put into a beaker, and a fixed amount of calcium carbonate (solid) was put into these beakers, and the amount of calcium carbonate dissolved per predetermined time was measured while stirring slowly (about 30 revolutions per minute). The results are shown in Table 2. 11298pif.doc / 008 10 1232237 [Table 2] Time from the start of the test (g) 5 minutes 10 minutes 15 minutes 20 minutes Example 1 12 20 24 29 Example 2 11 18 20 22 Example 3 11 18 20 22 Example 4 11 18 20 22 Example 5 10 17 18 20 Example 6 10 17 18 20 Example 7 10 15 17 19 Comparative Example 1 15 25 30 40 Comparative Example 2 5 10 12 15 Comparative Example 3 5 10 12 15 Comparative Example 4 7 12 15 18 Comparative Example 5 3 7 9 10 (3) The metal elution prevention performance is to evaluate the corrosion resistance of the cleaning target by the cleaning solution, and to measure the titanium from the cleaning target by cleaning. (Titanium) ion dissolution. The cleaning object is a steel plate having a shape of 15 cm X 15 cm X 6 mm (JISSS41: rolled steel plate for general structure). The test temperature is 20 ° C. The amount of dissolution of titanium ions was measured from the beginning of the experiment by 1 hr, 24 hrs, 48 hrs, and 12 hrs, respectively, by inductively coupled plasma emission spectrometry. The results are shown in Table 3. 11298pif.doc / 008 11 1232237 [Table 3] Time from dissolution of titanium ion (β g / ml) lhr 24hrs 48hrs 120hrs Example 1 < 0.1 < 0.1 < 0.1 < 0.1 Example 2 < 0.1 < 0.1 < 0.1 < 0.1 Example 3 < 0.1 0.18 0.25 0.30 Example 4 < 0.1 0.16 0.21 0.25 Example 5 < 0.1 0Λ5 0.20 0.22 Example 6 < 0.1 0.16 0.21 0.25 Example 7 < 0.1 0.16 0.21 0.25 Comparative Example 1 < 0.1 0.30 0.40 0.55 Comparative Example 2 < 0.1 < 0.1 < 0.1 < 0.1 Comparative Example 3 < 0.1 < 0.1 < 0.1 0.10 Comparative Example 4 < 0.1 < 0.1 < 0.1 0.15 Comparative Example 5 < 0.1 < 0.1 < 0.1 < 0.1 (4) Hydrogen embrittlement prevention performance The hydrogen embrittlement of the cleaning solution on the cleaning object was evaluated, and the titanium test piece was immersed in After one week of the cleaning solutions of Examples 1 to 7 and Comparative Examples 1 to 5, the following repeated stress load test was performed on the test piece to measure the number of times of stress load when the test piece was cracked. The test piece was a titanium metal plate having a size of 2 mm (thickness) x 20 mm (width) x 100 mm (length). The repeated stress loading test was made by fixing one end of a titanium metal plate immersed in the cleaning solution to a cantilever beam type. A round rod with a diameter of 10 mm was used as the pressing rod. The pressing pressure was about 2 kg and the stroke width was 2 mm. The test temperature was 20 ° c. The pressure of 11298pif.doc / 008 12 1232237 was 1 time / second, and the force was repeatedly applied at about 25 mm from the other end of the titanium metal plate to the hawk force. The test system continued until cracks were visually recognized in the titanium metal plate. The less the number of stress loads required until cracking occurs, the greater the material degradation of the titanium metal plate at risk from hydrogen J. In other words, the more the number of stress loads required for the occurrence of cracking, the higher the hydrogen embrittlement prevention ability of the cleaning solution. [Table 4] The test results are shown in Table 4. Number of stress loads to the occurrence of crack Example 1 3525 Example 2 3530 Example 3 3550 Example 4 3510 Example 5 3580 Example 6 2815 Example 7 2803 Comparative Example 1 3550 Comparative Example 2 1800 Comparative Example 3 1815 Comparison Example 4 2500 Comparative Example 5 1800 (5) Results From the above experimental results, when using a 100% sulfamic acid detergent (Comparative Example 1), although the problem of hydrogen embrittlement can be avoided, the amount of metal (titanium) ion dissolution is extremely low. Many are not suitable as detergents. In addition, when using the 100% citric acid cleaning agent 11298pif.doc / 008 13 1232237 (Comparative Example 5), although the amount of metal elution is reduced, the decrease in cleaning power is large, and hydrogen embrittlement is easily generated. 'Not suitable for Detergents for metal products for the purposes of the present invention. Furthermore, 'for the sulfamic acid-hydroxycarboxylic acid-based cleaning agents of Comparative Examples 2 to 4 having a composition different from the present invention', although the cleaning power is improved to a certain extent, and the amount of metal eluted is small, it is caused by hydrogen. The brittleness relationship cracks with a small number of stress loads. These results indicate that the combined composition of the comparative example cannot provide an excellent cleaner having all three characteristics of ① cleaning power, ② metal elution preventing ability, ③ hydrogen embrittlement preventing ability. In contrast, the results of Examples 1 to 7 indicate that a cleaning agent having an excellent ability to suppress hydrogen embrittlement and metal elution while maintaining high cleaning power can be provided within the composition range of the present invention. The cleaning agent produced by the combination of Example 1 and Example 2 is composed of a majority (more than 80%) of sulfamic acid, and the remaining portion is composed of equal amounts of citric acid and malic acid. At the same time, in order to maintain the cleaning power of about 70% or more in the case of using 100% sulfamic acid detergent, the amount of metal ions is reduced to less than 1/5, and the ability to prevent hydrogen embrittlement is reduced. The result is equivalent to that of 100% sulfamic acid detergent. Therefore, it can maintain the high cleaning power and hydrogen embrittlement prevention ability of 100% sulfamic acid detergent, and can overcome the low metal dissolution prevention performance of 100% sulfamic acid detergent. The detergent having the compounding composition of Example 1 or Example 2 of the present invention, that is, the detergent having a mixing ratio of sulfamic acid: citric acid: malic acid of 80 to 95: 10 to 2.5: 10 to 2.5 is should. Although the present invention has been disclosed as above with a preferred embodiment, it does not use 11298pif.doc / 008 t 14 1232237 to limit the present invention. Anyone skilled in the art can make the present invention without departing from the spirit and scope of the present invention. With some changes and retouching, the scope of protection of the present invention shall be determined by the scope of the attached patent application. 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