508375 經濟部智慧財產局員工消費合作社印製 A7 B7_五、發明說明（1 ) 本發明係有關用於鋼板、鍍鋅鋼板、銘材料之類的各 種金屬材料的鹼脫脂劑，及其使用方法，換言之，可以省 去一般磷酸鹽之化學表面處理系中，於鹼脫脂步驟與化學 表面處理步驟之間被施行之水洗步驟，或後述之表面調整 步驟的金屬材料之脫脂及化學表面處理方法者。 現今，爲提高各種金屬材料塗敷後之耐腐蝕性、緊貼 性及潤滑性，常常配合其用途施行各種磷酸鹽化學表面處 理。一般之磷酸鹽化學表面處理步驟係依順序進行（1 ) 鹼脫脂（2 )水洗、（3 )磷酸鹽化學表面處理、（4 ) 水洗、（5 )乾燥者，惟（2 )及（4 )之水洗步驟有時 必須視其需要施行多階段處理，或熱水洗步驟。又，有時 爲使其能適應塗敷底材之用，期能形成均勻且緻密之化學 表面處理被膜結晶，還做爲（3 )之前步驟施予表面活化 處理（表面調整處理）。又，被施予磷酸鹽處理之被處理 金屬材料之表面，通常均附著油份，這時（1 )之脫脂步 驟乃成一必要之步驟。 通常磷酸鹽化學表面處理步驟所用上述脫脂步驟中係 使用以界面活性劑，與確保脫脂性用而被添加之鹼成膜塡 充劑爲主成份之處理液。鹼脫脂處理液所用界面活性劑係 使用對油份具有優異之乳化性及防止油份再附著性之類型 者。脫脂處理液中之界面活性劑係具有可以乳化分散以除 去被處理金屬材料附著之油份，使乳化分散之油份不再附 著於金屬表面之效果。根據推測，可防止乳化分散之油份 再附著於金屬表面之機作應爲界面活性劑能以單分子之水 (讀先閱ff面之注意事項508375 Printed by A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (1) The present invention is an alkali degreasing agent for various metal materials such as steel plates, galvanized steel plates, and inscription materials, and a method for using the same In other words, in the general chemical surface treatment system of phosphate, a water washing step performed between the alkali degreasing step and the chemical surface treatment step, or a metal material degreasing and chemical surface treatment method in the surface adjustment step described later can be omitted. . At present, in order to improve the corrosion resistance, adhesion and lubricity of various metal materials after coating, various phosphate chemical surface treatments are often performed in accordance with their uses. The general phosphate chemical surface treatment steps are performed in order (1) alkaline degreasing, (2) water washing, (3) phosphate chemical surface treatment, (4) water washing, (5) drying, but (2) and (4) The water washing step may sometimes require a multi-stage treatment, or a hot water washing step, as required. In addition, in order to make it suitable for coating substrates, a uniform and dense chemical surface treatment film may be formed, and it may also be subjected to a surface activation treatment (surface adjustment treatment) as the previous step (3). In addition, the surface of the treated metal material to which the phosphate treatment is applied usually has an oil content attached thereto. At this time, the degreasing step (1) becomes a necessary step. Generally, in the above degreasing step used in the phosphate chemical surface treatment step, a treatment liquid containing a surfactant and an alkali film-forming filler which is added for ensuring degreasing properties is used as a main component. The surfactant used in the alkaline degreasing treatment liquid is a type which has excellent emulsifying property with respect to oil and prevents re-adhesion of oil. The surfactant in the degreasing treatment liquid has the effect of being able to emulsify and disperse to remove the oil attached to the metal material being treated, so that the emulsified and dispersed oil no longer adheres to the metal surface. According to speculation, the machine that can prevent the emulsified and dispersed oil from re-adhering to the metal surface should be a surfactant that can use a single molecule of water (read the precautions on the ff side)
本頁) •‘訂·. 本紙張&度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4- 508375 A7 經濟部智慧財產局員工消費合作社印製 B7__五、發明說明G ) 平吸附於被脫脂過的金屬表面，以防止油份再附著於金屬 表面所致。因此在界面活性劑吸附於金屬表面之下，使其 與磷酸鹽化學表面處理液接觸時，界面活性劑會抑制化學 表面處理反應之開始反應的底材金屬蝕刻反應，而阻礙化 學表面處理反應，所以以往均需要在脫脂後進行水洗步驟 〇 又，以往之鹼脫脂處理液通常係爲使硬水中，或使混 入之C a 2 +、Mg2 +等多價陽離子予以鉗合化，防止界面 活性劑之不溶化爲目的而含有多量之矽酸鹽或縮合磷酸鹽 等無機成膜塡充劑，或含有機鉗合化劑。上述成份若混入 磷酸鹽化學表面處理液中時會吸附於金屬表面，不但會阻 礙蝕刻反應，甚至還會鉗合化.碟酸鹽化學表面處理液中磷 酸鹽轉化形成被膜之主要成份的Ζ η 2 +，或爲提高耐腐性 而被添加予磷酸鹽化學表面處理液中的N i 2 +及Μη2 +等 陽離子成份，而阻礙磷酸鹽化學形成被膜結晶的析出。 爲防止上述問題發生，以往之化學表面處理系中必須 在鹼脫鹼處理後設置水洗步驟，將帶入磷酸鹽化學表面處 理步驟中之鹼脫脂處理液濃度稀釋爲不成問題之水準。爲 此鹼脫脂處理後之水洗步驟中必須隨時供給新鮮之操作用 水，保持一定之水質。又，經常供水時溢出之水洗水會被 送至廢水處理設備，提高供水及廢水處理成本，極不合乎 經濟原則。 又，以住最常被使用之鹼脫脂處理液係含有聚氧化乙 烯壬基苯醚等聚氧化烯烷基苯醚非離子界面活性劑者。惟 (讀先閱讀赛面之注意事項(This page) • 'Order ·. This paper & degree applies to China National Standard (CNS) A4 specification (210 X 297 mm) -4- 508375 A7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7__V. Description of the invention G) Flat adsorption on the degreased metal surface to prevent oil from re-adhering to the metal surface. Therefore, when the surface active agent is adsorbed under the metal surface and brought into contact with the phosphate chemical surface treatment solution, the surface active agent can inhibit the substrate metal etching reaction that starts the chemical surface treatment reaction, and hinder the chemical surface treatment reaction. Therefore, in the past, it was necessary to perform a water washing step after degreasing. In the past, the alkaline degreasing treatment solution was usually used to harden water or to mix mixed polyvalent cations such as Ca 2 + and Mg 2 + to prevent surfactants. For the purpose of insolubilization, it contains a large amount of inorganic film-forming fillers such as silicates or condensed phosphates, or contains a mechanical clamp compound. If the above components are mixed into the phosphate chemical surface treatment liquid, they will be adsorbed on the metal surface, which will not only hinder the etching reaction, but even clamp the chemical. The phosphate in the dishate chemical surface treatment liquid transforms to form the main component of the film. 2+, or cationic components such as Ni 2 + and Mn 2 + added to the phosphate chemical surface treatment liquid to improve the corrosion resistance, and prevent the precipitation of phosphate crystals from forming a film. In order to prevent the above problems, in the conventional chemical surface treatment system, a water washing step must be provided after the alkali dealkaliization treatment, and the concentration of the alkali degreasing treatment liquid brought into the phosphate chemical surface treatment step should be diluted to a non-problematic level. For this washing step after alkaline degreasing, fresh operating water must be supplied at any time to maintain a certain water quality. In addition, the washing water that overflows during regular water supply will be sent to wastewater treatment equipment, which raises the cost of water supply and wastewater treatment, which is extremely uneconomical. In addition, the most commonly used alkali degreasing treatment liquids are those containing a polyoxyalkylene alkylphenyl ether nonionic surfactant such as polyoxyethylene nonylphenyl ether. However, (Notes on reading the first reading surface)
本頁) :訂· ;線· 本紙張瓦度適闬中國國家標準（CNS)A4規格（210 公釐） -5- 508375 A7 B7 五、發明說明6 ) 此聚氧化烯烷基苯醚非離子界面活性劑係做爲對人類內分 泌會有所影響而引起世人之重大關心者，所以極希望能開 發可以替代其之界面活性劑，甚至開發出對環境保護不會 有問題之脫脂處理液。惟至今仍末有可以省去鹼脫脂後之 水洗步驟，即使被帶入其後之磷酸鹽化學表面處理液中亦 不會阻礙化學表面處理性之不屬於聚氧化烯烷基苯醚的界 面活性劑者，至少此等尙未爲人所熟悉，而且還沒有人知 道使用其之金屬材料的脫脂及化學處理方法。 本發明係以提供可以將以往之技術中被認爲極難之鹼 脫脂步驟與磷酸鹽化學處理步驟之間必須進行的水洗步驟 省去，即使鹼脫脂液被帶進其後之磷酸鹽化學表面處理液 中亦不會阻礙化學表面處理或發生弊害，且環保上沒有問 題之金屬材料鹼脫脂處理液，及其使用之方法，即，使用 其之金屬材料的脫脂及化學表面處理方法爲目的者。 本發明人等係針對解決上述之各問題的方法深入硏究 ，發現使用含特定構造之界面活性劑的鹼脫脂處理液予以 洗淨金屬表面後，立即使其與磷酸鹽化學表面處理液接觸 時，可以顯著縮短脫脂處理〜化學表面處理之步驟，遂而 完成本發明。 本發明係一種金屬材料之鹼脫脂處理液，其特徵爲含 有0 · 5〜8g/l HLB12〜17之聚氧化乙烯烷 基醚，至少一種之鹼金屬鹽及銨鹽，以及水，並且總鹼度 爲1〜1 5度之pH爲8〜1 3者，以及一種金屬材料之 脫脂及化學表面處理方法，其特徵爲使金屬材料與該鹼脫 本紙張瓦度適用中國國家標進（CNS)A4規格（210 X 297公釐） (請先閱讀脊面之注意事項本頁) :訂. --線_ 經濟部智慧財產局員工消費合作社印製 -6- 508375 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明4 ) 脂處理液接觸後，不必經水洗’使其與磷酸鹽化學表面處 理液接觸，以形成磷酸鹽被膜者。 另外，該鹼脫脂處理液係以再含有至少一種之二價或 三價金屬離子的磷酸鹽粒子’粒徑爲5 //m以下粒子爲宜 ，更以該鹼脫脂處理液爲含有〇 · 01〜30g/i之至 少一種磷酸鹽，該二價或三價之金屬離子爲至少一種選自 Zn2 +、Ni2 +、Mn2 +、Co2 +、Fe2 +、Ca2 +、 A 1 3+及F e 3 +爲最佳，並且該鹼脫脂處理液以含有鈦爲 0.001〜5g/l之鈦膠體爲宜。 其次，詳細說明本發明之內容。 在此說明本發明中使用之鹼脫脂處理液成份。首先說 明第一成份之界面活性劑。可適用於本發明之界面活性劑 係具有優異之乳化性，且被帶入其後之步驟的磷酸鹽化學 表面處理液中亦不會影響化學轉化性之特性者。又，環保 問題上被世人重視之對人類內分泌影響有問題的以往鹼脫 脂處理液中廣泛被使用之聚氧化乙烯壬基苯醚等聚氧化烯 烷基苯醚非離子界面活性劑完全未包含於其中。 本發明中所用界面活性劑必須爲聚氧化乙烯烷基醚、 更必須爲藉由聚氧化乙烯之加成莫爾數，烷基之碳數而被 決定之HL B爲1 2〜1 7範圍內的聚氧化乙烯烷基醚。 此物在此被發現對油份具有強力之乳化分散性，但對被處 理金屬表面之吸附力卻比其他非離子系界面活性劑更小。 即，H L B雖相同，若親油基之分子量大時，必須多 附加親油基。例如聚氧化乙烯壬基苯醚係因分子鏈中具有 (請先閒讀背面之注咅？事項寫本頁) Ϊ裝 · i線- 本紙張&度適用中國國家標進（CNS)A4規格（210 X 297公釐） 508375 Α7 Β7 五、發明說明6 ) 親油基之苯環與壬基，對油份之親和力強，但爲使油份乳 化分散於水溶液中，必須附加相對應量之聚氧乙烯於親油 基。惟在此聚氧化乙烯鏈太長時因會加大對金屬之吸附力 ，所以在脫脂處理後若不施予水洗處理，被認爲會阻礙磷 酸鹽化學表面處理反應。 本發明中使用之聚氧化乙烯烷基醚係做爲親油基只有 烷基、且親油基之分子量比聚氧化乙烯烷基苯醚非離子界 面活性劑小，環氧乙烯之附加莫爾數亦較少，所以具有對 金屬之吸附力小的特性。爲此在鹼脫脂處理液中可以充分 發揮防止油份再附著之效果，不但如此，即使附著於金屬 表面之下施予磷酸鹽化學表面處理，也可以在化學表面處 理液中的蝕刻反應時極易於脫離，完全不會阻礙磷酸鹽之 化學表面處理液反應。 經濟部智慧財產局員工消費合作社印制衣 爲使親水基與親油基平衡，即，爲使藉由聚氧化乙烯 之附加莫爾數與烷基之碳數予以決定的H L B値在特定範 圍，烷基之碳數以6〜2 0爲宜，更以8〜1 2爲最佳。 具體言可爲例如聚氧化乙烯己醚、聚氧化乙烯庚醚、聚氧 化乙烯辛醚、聚氧化乙烯壬醚、聚氧化乙烯癸醚、聚氧化 乙烯十一烷醚、聚氧化乙烯十二烷醚等。此等可單獨使用 ，亦可組合使用。又，除此外還可以含有聚氧化乙烯丙醚 、聚氧化乙烯丁醚等碳數爲6以下之烷基者，只要整體而 言H L Β在所定範圍內即可。 如上述，聚氧化乙烯烷基醚之HL Β必須爲1 2〜 1 7。H L Β爲1 2以下時會降低乳化分散能力，而降低 -8 - 本紙張尺度適用中國國家標屢（C7n：S)A4規格（210x 297公釐） 7 3 8 ο A7 _ B7 五、發明說明6 ) 脫脂性。又，H L B爲1 7以上時會提高吸附於金屬表面 之能力，在磷酸鹽化學表面處理時會阻礙蝕刻反應，而無 法得到均勻之被膜。 又，爲維持鹼脫脂處理液之良好脫脂性、聚氧化乙儲 烷基醚之濃度必須調整爲0 · 5〜8 g / 1之範圍，以調 整爲1〜7g/l較佳。濃度爲0 .5g/l以下時無法 確保良好之脫脂性。又，濃度爲8 g / 1以上時使處理液 與被處理物接觸雖不會影響脫脂性，但成本會增加造成浪 費，還會增加廢水處理時的負擔，所以不適宜。 又，本發明所使用聚氧化乙烯烷基醚係具有生物分解 性者，對環境保護而言係爲極佳之界面活性劑。 本發明中鹼脫脂處理液的第二成份之鹼金屬鹽或銨鹽 係使用一般之鹼脫脂劑所用者亦無妨者。根據推測，鹼金 屬鹽或銨鹽之作用可爲如下者。 (1 )可降低附著於被處理物（金屬材料）上之油份 的表面張力，提高界面活性劑之界面活性能力。 (2 )可微細乳化分散油份，使其更易於被包入微膠 粒中。 (3 )使油份粒子分散，防止其再附著於被處理物。 (4 )鉗合化鈣、鎂等多價陽離子成份，防止界面活 性劑成不溶化。 (5 )保持液體之鹼性，油份爲油脂時使其成爲可溶 性（皂化）。^ 只要可具有上述效果之鹼金屬鹽或銨鹽即可，例如可 本紙張尺度適用中國國家標準（CNS)A-l規格（210 X 297公釐） (請先閱背面之注意事項 Μ本頁) 經濟部智慧財產局員工消費合作社印剩衣 -9 - 508375 A7(This page): Order ·; Line · This paper is suitable for Chinese National Standard (CNS) A4 specifications (210 mm) -5- 508375 A7 B7 V. Description of the invention 6) This polyoxyalkylene alkyl phenyl ether is non-ionic As a major concern to the world, surfactants have an impact on human endocrinology. Therefore, it is highly hoped that they can develop surfactants that can replace them, and even develop degreasing treatment solutions that will not cause problems for environmental protection. However, there is still no water washing step after alkali degreasing, and even if it is brought into the subsequent phosphate chemical surface treatment solution, it will not hinder the chemical surface treatment of non-polyoxyalkylene alkyl phenyl ether interface activity. At least these agents are not familiar, and no one knows the degreasing and chemical treatment methods of the metal materials using them. The present invention is to provide a water washing step which must be performed between the alkali degreasing step and the phosphate chemical treatment step which have been considered extremely difficult in the prior art, even if the alkali degreasing liquid is brought into the subsequent phosphate chemical surface The treatment liquid does not hinder chemical surface treatment or cause harm, and there is no environmental protection problem for the metal material alkali degreasing treatment liquid, and the method for using the same, that is, the degreasing of the metal material and the chemical surface treatment method are used for the purpose . The present inventors have intensively studied the methods for solving the above problems, and found that when the metal surface is washed with an alkaline degreasing treatment solution containing a surfactant with a specific structure, it is immediately brought into contact with a phosphate chemical surface treatment solution. The steps of degreasing treatment to chemical surface treatment can be significantly shortened, and the present invention is completed. The present invention is an alkali degreasing treatment liquid for metal materials, which is characterized by containing 0.5 to 8 g / l HLB 12 to 17 polyoxyethylene alkyl ether, at least one kind of alkali metal salt and ammonium salt, and water, and total alkali. Those with a degree of 1 to 15 and a pH of 8 to 13 and a method for degreasing and chemical surface treatment of metal materials, characterized in that the wattage of the metal material and the alkaline degreasing paper are applicable to China National Standards (CNS) A4 size (210 X 297 mm) (please read the ridges precautions page first): Order. --Line_ printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives-6- 508375 Α7 Β7 employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative V. Description of the invention 4) After contacting the lipid treatment liquid, it is not necessary to wash it to contact the phosphate chemical surface treatment liquid to form a phosphate coating. In addition, the alkali degreasing treatment liquid is preferably particles that further contain at least one kind of divalent or trivalent metal ions, and the particle diameter is 5 // m or less, and the alkali degreasing treatment liquid contains 0.01 ~ 30g / i at least one phosphate, the divalent or trivalent metal ion is at least one selected from Zn2 +, Ni2 +, Mn2 +, Co2 +, Fe2 +, Ca2 +, A 1 3+ and F e 3 + Is the best, and the alkaline degreasing treatment liquid preferably contains a titanium colloid containing 0.001 to 5 g / l of titanium. Next, the contents of the present invention will be described in detail. Here, the components of the alkali degreasing treatment liquid used in the present invention will be described. First, the surfactant of the first component will be described. The surfactants applicable to the present invention have excellent emulsifying properties, and are not affected by the chemical conversion properties by being brought into the phosphate chemical surface treatment liquid in the subsequent steps. In addition, non-ionic surfactants such as polyoxyalkylene nonyl phenyl ether, such as polyoxyethylene nonylphenyl ether, which are widely used in conventional alkaline degreasing treatment fluids, which have been paid attention to environmental issues and have an impact on human endocrine, are not included at all. among them. The surfactant used in the present invention must be a polyoxyethylene alkyl ether, and the HL B determined by the addition mole number of polyoxyethylene and the carbon number of the alkyl group must be in the range of 1 2 to 17 Polyoxyethylene alkyl ether. This material was found to have strong emulsifying and dispersing properties to oil, but its adsorption force to the treated metal surface was smaller than that of other non-ionic surfactants. That is, although H L B is the same, if the molecular weight of the lipophilic group is large, it is necessary to add more lipophilic group. For example, polyoxyethylene nonylphenyl ether is based on the molecular chain (please read the note on the back? Please write this page) Outfitting · i-line-This paper & degree applies to China National Standards (CNS) A4 specifications (210 X 297 mm) 508375 A7 B7 V. Description of the invention 6) The benzene ring and nonyl group which are lipophilic have a strong affinity for oil, but in order to emulsify and disperse the oil in the aqueous solution, a corresponding amount must be added. Polyoxyethylene is lipophilic. However, when the polyethylene oxide chain is too long, the adsorption force on the metal will be increased. Therefore, if the water-washing treatment is not performed after the degreasing treatment, it is considered that it will hinder the chemical surface treatment of phosphate. The polyoxyethylene alkyl ether used in the present invention has only alkyl groups as the lipophilic group, and the molecular weight of the lipophilic group is smaller than that of the polyoxyethylene alkylphenyl ether nonionic surfactant, and the additional mole number of the ethylene oxide It also has a small amount, so it has a small adsorption force to metals. For this reason, the effect of preventing re-adhesion of oil can be fully exerted in the alkali degreasing treatment solution. Not only that, even if phosphate chemical surface treatment is applied under the metal surface, it can also be used during the etching reaction in the chemical surface treatment solution. Easily detached and does not hinder the reaction of phosphate chemical surface treatment liquid. In order to balance the hydrophilic group with the lipophilic group, that is, to make the HLB determined by the additional mole number of polyethylene oxide and the carbon number of alkyl group in a specific range, The carbon number of the alkyl group is preferably 6 to 20, and more preferably 8 to 12. Specifically, it can be, for example, polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene undecyl ether, polyoxyethylene dodecyl ether Wait. These can be used alone or in combination. In addition, it may contain alkyl groups having a carbon number of 6 or less, such as polyoxyethylene propylene ether and polyoxyethylene butyl ether, as long as H L B is within a predetermined range as a whole. As described above, the HL B of the polyoxyethylene alkyl ether must be 12 to 17. When HL Β is less than 1 2 it will reduce the emulsifying and dispersing ability, and decrease -8-This paper size is applicable to Chinese national standard (C7n: S) A4 specification (210x 297 mm) 7 3 8 ο A7 _ B7 V. Description of the invention 6) Degreasing. In addition, when H L B is 17 or more, the ability to be adsorbed on the metal surface is increased, and the etching reaction is hindered during phosphate chemical surface treatment, so that a uniform film cannot be obtained. In order to maintain the good degreasing performance of the alkaline degreasing treatment solution, the concentration of the polyethylene oxide alkyl ether must be adjusted to a range of 0.5 to 8 g / 1, and preferably to 1 to 7 g / l. When the concentration is 0.5 g / l or less, good degreasing properties cannot be ensured. In addition, when the concentration is 8 g / 1 or more, contacting the treatment liquid with the object to be treated does not affect the degreasing property, but the cost is increased and the burden on waste water treatment is increased, so it is not suitable. In addition, the polyoxyethylene alkyl ethers used in the present invention are biodegradable and are excellent surfactants for environmental protection. The alkali metal salt or the ammonium salt of the second component of the alkali degreasing treatment liquid in the present invention is not limited to those used in general alkali degreasing agents. It is speculated that the effects of alkali metal salts or ammonium salts may be as follows. (1) It can reduce the surface tension of the oil attached to the object to be treated (metal material), and improve the interfacial activity of the surfactant. (2) It can finely emulsify and disperse the oil, making it easier to be encapsulated in the micelles. (3) The oil particles are dispersed to prevent them from re-adhering to the object to be treated. (4) Clamping polyvalent cation components such as calcium and magnesium to prevent the surfactant from becoming insoluble. (5) Keep the alkalinity of the liquid, and make it soluble (saponification) when the oil is fat. ^ As long as the alkali metal salt or ammonium salt can have the above effects, for example, this paper size can be applied to the Chinese National Standard (CNS) Al specification (210 X 297 mm) (please read the precautions on the back page) Ministry of Intellectual Property Bureau Employees' Cooperatives Printing Leftovers-9-508375 A7
五、發明說明f ) 爲磷酸鹽（包含磷酸氫鹽在內）、碳酸鹽、碳酸氫鹽、硫 酸鹽（含硫酸氫鹽在內）、硼酸鹽、亞硝酸鹽類型者。又 ，鹼金屬可爲鈉、鉀、鋰。具體言，較佳之鹼金屬鹽或銨 鹽可爲例如磷酸鈉（或鉀或銨）、磷酸氫二鈉（或鉀或錢 )、碳酸鈉（或鉀或銨）、碳酸氫鈉（或鉀或銨）、硫酸 鈉（或鉀或銨）、硼酸鈉（或鉀或銨）、亞硝酸鈉（或鉀 或）銨等。 又’磷酸鹽化學表面處理液中即使混合入具有與上述 驗金屬鹽、或銨鹽同樣作用之縮合磷酸鹼鹽（二磷酸鈉、 三磷酸鈉等聚磷酸鹼鹽、偏磷酸鹼鹽等）及/或矽酸鹼鹽 (砂酸鈉等），只要在不阻礙化學表面處理性之範圍的量 亦可以倂用。即，本發明之鹼脫脂處理液中之縮合磷酸鹼 鹽及矽酸鹼鹽之合計濃度係以〇〜5 g / 1爲宜，較佳爲 請 閱 面 意 事 項5. Description of the invention f) For phosphate (including hydrogen phosphate), carbonate, bicarbonate, sulfate (including hydrogen sulfate), borate, and nitrite types. The alkali metal may be sodium, potassium, or lithium. Specifically, the preferred alkali metal or ammonium salt may be, for example, sodium phosphate (or potassium or ammonium), disodium hydrogen phosphate (or potassium or ammonium), sodium carbonate (or potassium or ammonium), sodium bicarbonate (or potassium or Ammonium), sodium sulfate (or potassium or ammonium), sodium borate (or potassium or ammonium), sodium nitrite (or potassium or ammonium), etc. In addition, even if a phosphate chemical surface treatment liquid is mixed with a condensed alkaline phosphate salt (such as a polyphosphate alkaline salt, a metaphosphate basic salt, etc.) that has the same effect as the metal detection salt or ammonium salt, and The alkali silicate (sodium oxalate, etc.) may be used in an amount in a range that does not impede the chemical surface treatment. That is, the total concentration of the condensed phosphate alkali salt and the silicic acid alkali salt in the alkali degreasing treatment liquid of the present invention is preferably 0 to 5 g / 1, and more preferably, please refer to the notice item
Η 頁 I 經濟部智慧財產局員工消費合作社印製 0 〜3 g / 1。 有關鹼金屬鹽或 理液之p Η値必須調 。又，完全省略鹼脫 1〜1 3度爲宜，更 或總鹼度爲1度以下 pH爲13以上或總 液進入磷酸鹽化學表 理液之安定性，無法 以並不適宜。 在此所稱鹼脫脂 銨鹽之濃度方面，本發明 整爲8〜1 3，總鹼度爲 脂步驟後之水洗步驟時， 以2〜10度爲最佳。P 時無法得到令人滿意之脫 鹼度爲1 5度以上時，若 面處理液中會阻礙磷酸鹽 順利進行磷酸鹽被膜之析 之鹼脫脂處 1〜1 5度 總鹼度係以 Η爲8以下 脂性。又， 鹼脫脂處理 化學表面處 出反應，所 處理液之總鹼度係指取1 〇 m 1鹼脫 線 本紙張尺度適用中國國家標進（CNS)A4規格（210 X 297公釐） 10- 508375 Α7 Β7 經濟部智慧財產局員工消費合作社印制农 五、發明說明6 ) 脂處理液，加入溴酚鹽藍爲指示藥，以0 · 1 N之硫酸水 溶液進行中和滴定，以自藍色變爲黃色爲止所需滴定液之 m 1數來表示者。例如總鹼度1度係指上述m 1數爲1 m 1者。 本發明鹼脫脂處理液的第三成份之水可使用純水或脫 離子水、自來水等。 鹼脫脂後，形成塗敷底材用磷酸鹽化學表面處理被膜 時，最好使其析出約2〜5 g/m2左右被膜重量之均勻， 且緻密薄膜型的磷酸鹽被膜爲宜。爲此以往係通常在鹼脫 脂後，以表面調整劑施行表面調整處理後再進行塗敷底材 用磷酸鹽化學表面處理，但本發明中卻發現只要在本發明 之鹼脫脂處理液中添加倂用表.面調整劑，即可滿足脫脂效 果與表面調整效果之雙方效果。 表面調整劑可用至少一種二價或三價金屬離子之磷酸 鹽粒子，且粒徑爲5 // m以下之粒子。在此二價或三價金 屬離子係以至少一種選自鋅離子（Ζ η 2 + )、鎳（I I ) 離子（Ni2+)、鍤（I I)離子（Μη2+)、鈷（I I )‘離子（Co2+)、鐵（I I)離子（Fe2 + )、鈣離子 (C a 2 + )、鋁離子（A 1 3 + )及鐵（I I I )離子（ F e 3+)中者爲宜。二價或三價金屬離子之磷酸鹽係具體 曰可爲 Zll3(P〇4)2、 Zll2Fe (Ρ〇4)2、 Ζ η 2 N i (Ρ〇4)2、Ni3(p.〇4)2、 Ζη2Μη (Ρ〇4) 2、 Μη3 (ρ〇4) 2、 Μ η 2 F e (Ρ〇4)2、 Ca3(p〇4)2、 (誇先閱4背面之注意事項本頁) 裝 、訂· i線· 本紙張尺度適用中國國家標舉（CNS)A-l規格C210 X 297公爱） -11 - 508375 經濟部智慧財產局員工消費合作社印製 A7 B7____ 五、發明說明自) ζ η 2 C a (P〇4)2、 C〇3(P〇4)2、 A1P〇4、 F e P O 4等。此等亦可爲水合物者。 又，粒徑之下限並不特別限制，反而較小爲宜’惟就 製造之技術面，取得之容易性等實質上可取得方面考量以 〇· l//m左右爲宜。 表面調整劑亦可用鈦膠體。 本發明之鹼脫脂處理液中，使用時之表面調整劑的濃 度係至少爲一種二價或三價金屬離子之磷酸鹽時，必須爲 0 · 01 〜30g/l ，以 0 · 0 3 〜2〇g/l 爲宜， 以〇· 0 5〜1 0 g / 1爲較佳，最佳係〇 · 1〜1 〇 g / 1 ，鈦膠體時做爲鈦必須爲0 · 0 0 1〜5 g / 1 ’以 0·0〇5〜3g/l爲宜，更以0·05〜3g/l爲 最佳。各表面調整劑若低於上述下限値之濃度時無法得表 面調整效果，且無法得均勻且緻密之磷酸鹽化學表面處理 被膜。又，表面調整劑若超出上述上限濃度時，使金屬材 料與含表面調整劑之驗脫脂處理液接觸時該表面調整效果 已達飽和，所以不合經濟原則。 本發明中使用之鹼脫脂處理液中的聚氧化乙烯烷基醚 係金屬材料表面之吸附力弱，所以與表面調整劑倂用時會 從完成脫脂部份有表面調整效果之成份被吸附，顯示出優 異之表面調整效果。 另外，本發明之鹼脫脂處理液係除上述成份之外，還 可含有提高洗淨作用之補助添加劑。可含有例如可鉗合工 業用水中之陽離子成份（Co2 +、Mg2 +等），或溶離至 (請先閱ti#面之注意事項 --· I . 本頁 IT: |線· 本紙張尺度適用中國國家標準（CNS)A-l規格（210 X 297公釐） -12- 508375 A7 B7 五、發明說明6〇 ) 經濟部智慧財產局員工消費合作社印製 鹼脫脂處理液中之被處理金屬材料成份（Z n2 +、 A 1 3 +等）的胺基羧酸型、羥基羧酸型、膦酸型之鉗合劑 (例如乙二胺四乙酸鹽（鈉鹽等）、檸檬酸鹽（鈉鹽等） 、戊烯二酸鹽（鈉鹽等）、2 -膦酸丁烷三羧酸1，2， 4等）、或可防止一旦經由界面活性劑而脫去之油份再附 著於被處理金屬材料的羧甲基纖維素、羥丙基甲基纖維素 、羥丁基甲基纖維素等纖維素衍生物等亦無妨。使用此等 補助添加劑時必須以混入其後之磷酸鹽化學表面處理液中 亦不會發生問題之濃度範圍使用，惟若能形成爲正常之磷 酸鹽被膜’則對其配合量並不加以限制。通常，本發明之 鹼脫脂處理液中的鉗合劑濃度係1 g / 1以下爲宜，更佳 係0 . 0 1〜1 g / 1 ，考慮會混入其後之磷酸鹽化學表 面處理液中之問題時以0·01〜〇·5g/l爲更適宜 ，纖維素衍生物之濃度係以3 g / 1以下，更以〇 · 〇 1 〜3 g / 1爲宜，考慮會混入其後之磷酸鹽化學表面處理 液中之問題時’以0·01〜lg/丨爲更佳。 通常爲抑制洗淨作業時因發泡而發生問題，鹼脫脂處 理液中係包含消泡劑者，本發明之鹼脫脂處理液中亦可包 含消泡劑。此消泡劑可以自一般慣用者適當地選擇使用。 本發明之鹼脫脂處理液係將HLB12〜17之聚氧 化乙儲院基醚，至少一種之驗金屬鹽及錢鹽，以及有使用 時之表面調整劑（至少一種二價或三價金屬離子的磷酸鹽 粒子，粒徑爲5 // m以下者或鈦膠體），以及有使用時之 縮合憐酸鹼鹽、矽酸鹼鹽、補助添加劑、消泡劑等溶解或 (請先閱蜂¾^面之注意事項本頁) —裝 -訂· --線- 本紙m灵度過円宁國Μ豕知準規格（21〇 X 297公爱） 13- 經濟部智慧財產局員工消費合作社印製 508375 A7 B? 五、發明說明6ι ) 分散於水，即可調製而得。可用葉片攪拌等混合。又，總 鹼度及pH之調整可視其需要使用氫氧化鈉、氨水、磷酸 、硫酸等進行。 本發明之鹼脫脂處理液可使用於附著油份之金屬材料 的脫脂用。通常被施予磷酸鹽處理之金屬材料上係附著擠 壓、削切等前步驟中所用之油份。具體言，附著之油份係 機油、煤油、輕油、削切油劑、渦輪油、防銹油、擠壓油 、錠子油等。油份之附著量並不特別限制。另外，還可以 爲油份以外混入有鐵粉或其他污垢附著於其上者。 本發明之鹼脫脂處理液所適用之金屬材料種類並不特 別限制，可爲各種鋼鐵材料，例如鋼板（冷軋鋼板、熱軋 鋼板等）。鍍鋅鋼板（熔融鍍鋅鋼板、電鍍鋅鋼板、鍍含 鋁做爲合金成份之鍍鋅系鋼板等），以及各種鋁材料，例 如鋁板材及鋁合金（JIS 2000(Al-Cu-Mg)、5000 (A1- Mg)及 6000 (A1-Mg — S i )系合金等）材料等。對金屬材料之形狀亦不 特別限定。 本發明之鹼脫脂處理液係以噴霧式或浸漬法，於3 0 〜7 0 °C溫度施行3 0〜6 0 0秒，適用於附著油份之金 屬材料表面爲宜。 脫脂處理（此脫脂處理中可以如上述兼有表面調整處 ϊ里在內）後不經水洗，即可施予磷酸鹽化學表面處理，藉 此最能發揮本發明鹼脫脂處理液之特長。 惟代替以往鹼脫脂處理中之鹼脫脂處理液，使用本發 本紙張&度適闬中國國家標準（CNSM4規格（210 X 297公釐） -14- --------------裝--- (請先閱讀普面之注咅？事項寫本頁) 、訂： —線- 508375 A7 B7 五、發明說明62 ) 明之鹼脫脂處理液亦無妨。也就是說可使用本發明之鹼脫 脂處理液進行鹼脫脂、水洗、繼而進行磷酸鹽化學表面處 理，亦可以施予鹼脫脂、水洗、表面調整處理，繼而不經 水洗，進行磷酸鹽化學表面處理。 本發明亦爲使用本發明之鹼脫脂處理液的方法，即， 有關使金屬材料與本發明之鹼脫脂處理液接觸後，不經水 洗，再與磷酸鹽化學表面處理液接觸，以形成磷酸鹽化學 表面處理被膜爲特徵的金屬材料之脫脂及化學表面處理方 法。 使金屬材料與鹼脫脂處理液之接觸方法，其條件如上 述。本發明中係鹼脫脂處理後不必經水洗，即可施予磷酸 鹽化學表面處理者。 磷酸鹽化學表面處理可用一般公知或常用之磷酸鹽化 學表面處理液及處理條件（化學表面處理條件）進行。 不論其爲全部公知或常用者，在此舉一例說明。本發 明方法中所用磷酸鹽化學表面處理液係以磷酸鋅化學表面 處理液，更以基本上含有0 . 5〜20g/l鋅離子、 10〜50g/l磷酸離子及水，游離酸度0 · 5〜15 度之磷酸鋅化學表面處理液爲宜。更詳而言，使用於塗敷 用底材時，由所要求之被膜重量而言，磷酸鹽化學表面處 理液係以含有0.5〜5g/l鋅離子、10〜20g/ 1磷酸離子及水，游離酸度爲0.5〜4.0度爲宜，使 用在潤滑用底材或防銹被膜用時，由所要求之被膜重量而 言，磷酸鹽化學表面處理液係以含有5〜2 0 g/丨鋅離 (請先閱讀脅面之注意事項寫本頁) 裝 ，訂： 經濟部智慧財產局員工消費合作社印製 本紙張尺度適同中國國家標準（CNS)A4規格⑵0 X 297公釐） -15- 7 3 8ο A7 __;__B7__ 五、發明說明纟3 ) 子、10〜50g/l磷酸離子及水，游離酸度4.0〜 15度，尤其5.0〜13度爲宜。 在此鋅離子之供給來源可爲可溶於磷酸水溶液中之鋅 化合物，例如氧化鋅、磷酸鋅、硝酸鋅等，磷酸離子之供 給源可爲磷酸（原磷酸）等。 上述游離酸度由於欲極精確在極佳之重現性下測定2 〜3左右低p Η時很難以p Η測儀（玻璃電極）測出，所 以在此爲表示磷酸鹽化學表面處理液之酸性度，代替ρ Η 以一般使用之代用値，以採取1 〇 m 1磷酸鹽化學表面處 理液，以溴酚藍爲指示藥，以〇 . 1 N氫氧化鈉水溶液進 行中和滴定，自黃色變成藍色爲止所需滴定液的m 1數， 例如游離酸度1度係指上述m 1數爲1 m 1而言者。 本發明方法中所用磷酸鹽化學表面處理液在上述任一 用途使用時均可以含有爲提高酸之蝕刻力，促進化學表面 處理反應之化學表面處理促進劑，破壞金屬表面之氧化膜 ，以輔助蝕刻反應之蝕刻助劑，提高被膜之緊貼性或爲提 高對酸、鹼之化學安定性所用的其他金屬離子等。 化學表面處理促進劑可爲亞硝酸離子（以亞硝酸鈉等 供給）、羥基銨離子（以硫酸羥基銨等供給）、氯酸離子 (以氯酸鈉等供給）、硝基苯磺酸離子（以硝基苯磺酸鈉 等供給）、過氧化氫、有機過氧化物（以乙基過氧化氫、 異丙基過氧化氫等特開平8 - 3 0 2 4 7 7號公報所示者 等）等。化學表面處理促進劑通常以含〇·05〜2.0 g / 1濃度爲宜。 (請先閱讀脅面之注意事項 —-裝--- 寫本頁) -線· 經濟部智慧財產局員工消費合作社印製 本纸張Κ度適闬中國國家標準（CNS)A4規格（210 X 297公釐） -16- 經濟部智慧財產局員工消費合作社印制衣 508375 A7 B7 五、發明說明纟4 ) 鈾刻助劑係有氟化物離子、矽氟化物離子等。此等可 做爲鈉鹽、銨鹽或游離之酸（氟化氫酸、矽氟化氫酸等） 含於磷酸鹽化學表面處理液中。含有時鈾刻助劑之濃度係 以0·1〜2.0g/l爲宜。 其他金屬離子可以使用主要可以提高被膜緊貼性之鎳 離子（Νι2+)、銅離子（Cu2+)、鈷離子（C〇2 + )等及/或主要可提高被膜之化學安定性（耐酸性、耐鹼 性）的錳離子（Mn2+)、鎂離子（Mg2+)、鈣離子（ C a 2+)等。此等可做爲硝酸鹽、磷酸鹽含於磷酸鹽化學 表面處理液中。含有此其他金屬離子時其濃度係銅離子時 爲5〜50mg/l ，其他金屬離子係以〇·1〜3.〇 g / 1爲宜。 本發明方法中所用磷酸鹽化學表面處理液的調製方法 並無特別限制，通常只要將磷酸離子供給源、鋅離子供給 源，及視其需要之化學表面處理促進劑、蝕刻助劑及/或 其他金屬離子供給源等溶解於水使其成爲所定濃度即可調 製而成。 所調製之磷酸鹽化學表面處理液係可適用於不必經水 洗的藉由本發明之鹼脫脂處理液所處理之金屬材料。 使用該磷酸鹽化學表面處理液處理金屬材料時的處理 方法係以噴霧處理或浸漬處理爲宜。 這時之處理溫度，處理時間及被膜重量係視被膜用途 之不同而異。 將該磷酸鹽化學表面處理液用於形成塗敷用底材之被 本纸張汶度適闬中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注咅？事項寫本頁) 、訂· -·線. 508375 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明65 ) 膜用時’最好析出被膜重量爲2〜5 g/m2左右之薄膜型 的均勻且緻密之磷酸鋅被膜爲宜。處埋時之處理液溫度係 3 5〜6 0 °C爲宜，處理時間係以3 0秒鐘〜1 〇分鐘爲 宜。 使用該磷酸鹽化學表面處理液於形成潤滑底材之被膜 用時，以析出被膜重量爲5〜2 0 g/m2左右之厚膜型的 磷酸鋅被膜爲宜。處理時之處理液溫度係6 0〜9 Ot爲 宜，處理時間係以3 0秒〜1 0分鐘爲宜。 採用本發明之脫脂及化學表面處理方法時可以獲得具 有與以往所施行脫脂-水洗-（表面調整）-化學表面處 理-之一連串步驟所得磷酸鹽化學表面處理被膜一樣之外 觀，性能的磷酸鹽化學表面處理被膜。 磷酸鹽化學表面處理後，爲除去附著之磷酸鹽化學表 面處理液，金屬材料在此予以水洗或熱水洗。其後視其需 要乾燥後，欲塗敷時係施予塗敷處理，潤滑爲目的時則塗 敷反應型之皂處理或固體潤滑劑。防銹爲目的時通常係乾 燥後直接使用或塗佈防銹油。 其次，示實際處理之實施例與比較例具體說明本發明 之效果。另外，實施例僅係舉本發明之用途例，對本發明 之用途及適應之原材枓並不加任何限制。 1 ·試驗材料 使用冷軋鋼板（0.8mm板厚、SPCC - SD) ，兩面熔融鍍鋅鋼板（註冊商標·· Silver Alloy，新日本製 片^·-- (請先閱尊面之注意事項寫本頁) 言 Γ 良 本紙張尺度適用中國國家標進（CNSM.!規格（210 x 297公t ) -18- 508375 A7 ____B7^_ _ _ 五、發明說明66 ) 鐵公司製，板厚：0·8mm，鍍鋅附著量：一面爲45 g/m2)，鋁一鎂合金板（板厚：1 · 〇mm，J I S-A 5 0 5 2 )，施予下述實施例及比較例之處理。又，各 試驗材料係塗佈2 g /m 2市販之洗淨防銹油（註冊商標： Ν Ο X RUST 530 — 40，Parker 興產公司製） ，以1 0 0枚塗佈油板重疊堆置，以轉矩板手用轉矩壓力 70Kg f/Cm束緊，放置於60°C相對濕度95%以 上之濕潤箱內4天後再使用。 實施例及比較例中使用之鹼脫脂處理液之組成係如表 1、表2中所示。又，構成驗脫脂處理液之水係在表1、 表2省略其記載，惟水係使用自來水。 經濟部智慧財產局員工消費合作社印制农 -19- 本紙張尺度適用中國國家標車（CNS)A4規格（210 X 297公釐） 508375 五、發明說明67 ) 經濟部智慧財產局員工消費合作社印製 鹼脫脂處 理液6 聚氧化乙烯烷基醚 7g/l 16.6 VO Nl2HP〇4 12度 CS1 ON *2Brebalen ZN 以鈦而言 爲 o.lg/l m S5 ^ 邋勸 5g/l 16.6 un N a 2 C 0 3 (NH4)2S〇4 cn 10.3 Zn3(P〇4)2 • 4H2〇 ε cn lg/1 m m ^ m m 鎏刮 lg/1 14.3 oo N a 2 C 〇 3 Na2〇-Si〇2 侧 r— CN r—Η r· Η Zn2Fe9P〇4)2 • 4H2〇 ε $ un 2g/l 鹼脫脂處理 液3 2g/l 14.3 o Na2HP〇4 NaN〇2 侧 CS OO Zn2Fe(P〇4)2 • 4H2〇 ε $ i"1 i 5g/l m m ^ m m 鎏到 7g/l cn 寸 r" 1 i o N a3P〇4 (NH4)2S〇4 制 m un CN t—H 1 1 1 鹼脫脂處 理液1 2g/l cn csi 1—H oo Na3P〇4 Na4P2〇7 10度 CNl 1 1 1 種類 濃度 HLB E〇附加莫爾數 種類 總鹼度 pH値 種類 粒徑* i 濃度 界面 活性 m 表面 調整 成分 (Μίί?<4㈤.szpssd 柃ΕΠ:職輕繼 _)NZ ui qePQ: * 轵震(fM^e鉍ti ® : 026 — V Ί )酗鏘识Μ拒Φ倒^笊菡鎰\菡耀菡_旺钽：1* --------------裝--- (請先閱讀背面之注意事項寫本頁) ，訂· .線· 本紙張尺度適用中國國家標進（CNS)A4規格（210 X 297公釐） -20- 508375 A7 B7 五、發明說明68 ) ei_i 6髮勸0 mss 經濟部智慧財產局員工消費合作社印製 8髮爾 I ΐ®_ίοί® CSII m b艘婴裝纒 m 1 i DJQ r—Η τ—Η ν〇 ι—Η 〇 Ph rs οΰ z cn ο ON C <υ σ3 X) (D 一！Ζ PQ Γ： 〇, Ν3 * Hull g — ^ ¢1 c〇 K] ι 4 、^ bi) 寸 m 寸 ,_ 崎 ΟΟ •rr 〇 cu ΓΟ o3 z 姻 ο f Η ， ·Η OJ Ο Ρη 〇 U Κ ^ CSI CS C! 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Ornil P Μ « 虼K萌蘅 馨 嗽陌鼷_链Φ --------------裝— (請先閱尊面之注咅筆項本頁) •訂： -1線· 本紙張尺度適用中國國家標進（CN’S)A4規格（210x297公釐） 508375 Α7 五、發明說明（19 ) 2 .評估試驗方法 2.1 被膜重量 首先測化學表面處理後之處理板重量（以W 1 〔 g〕 表示），繼而使用下述剝離液’剝離條件對該化學表面處 理板施予被膜剝離.處理，測其重量（以w 2〔 g〕表示） ，使用式（1)算出被膜重量。 被膜重量〔g/m2〕= (W1 - W2 ) /處理物之表面積 剝離液，剝離條件 (1) 冷軋鋼板時 剝離液：5重量％鉻酸水溶液 剝離條件：7 5 °C，1 5分鐘浸漬剝離 (2) 兩面熔融鍍鋅鋼板時 剝離液：2重量％重鉻酸銨+28%氨水+49重 量％水 剝離條件：常溫，1 5分鐘浸漬剝離 (3 )鋁一鎂合金板時 剝離液：5重量％鉻酸水溶液 剝離條件：常溫，1 5分鐘，浸漬剝離 2.2 底板被覆性 使用掃描型電子顯微鏡（S E Μ )擴大析出被膜結晶 爲1 5 0 0倍進行觀察。依以下之基準自此擴大像評估底 本紙張尺度適用中國國家標車（CNS)A4規格（210 X 297公釐） 請先閱讀背面之注意事項本頁) 裝 •線· 經濟部智慧財產局員工消費合作社印製 -22- 508375 A7 經濟部智慧財產局員工消費合作社印制衣 B7_五、發明說明如 ） 板金屬之被覆性（有無底板露出）° 評估基準 完全未露出底板—〇（良好） 稍微露出底板 —△(稍差） 底板完全露出 一 x(極差） 2.3 以目視評外觀 依以下基準評估化學表面處理後之外觀。 評估基準 得均勻之成品，沒有化學表面處理不均勻或不佳處 —〇（良好） 稍有化學表面處理不均勻或不良之處—△(稍差） 整體言均有化學表面處理不均勻或不良之處—x ( 極差） 2 · 4化學表面處理液被膜之結晶粒徑 使用S E Μ擴大爲1 5 0 0倍求得。 2 · 5鹼脫脂液之脫脂性 於所定溫度使試驗材料與鹼脫脂處理液接觸所定時間 (與後述之各實施例、比較例中一樣之條件），立即進行 水洗（噴霧3 0秒），垂直放置1分鐘後，以目視觀察所 佔水濕面積，評估其脫脂性。 (請先閱讀背面之注意事項寫本頁) 裝 訂· --線_ 本紙張尺度適用中國國家標皋（CNS)A4規格（210 X 297公釐 -23- 508375 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明έι ) 實施例1 將鹼脫脂處理液1加溫爲4 5 °C，在其中浸漬冷軋鋼 板1 2 0秒鐘。其後不經水洗，溶解塑性加工潤滑前之底 材用磷酸鹽化學表面處理液（註冊商品：parb〇nd-181X日 本Parkenzing公司製）於自來水使其爲9〇g/l ，調製 成磷酸鹽化學表面處理液，於8 0 °C浸漬於該液5分鐘， 經水洗及純水洗，製作爲試驗板。 實施例2 將鹼脫脂處理液2加溫爲3 5 °C，對於冷軋鋼板噴霧 1 2 0秒鐘。其後不經水洗，溶解塑性加工潤滑前之底材 用磷酸鹽化學表面處理液（註冊商品：parbond-421WD曰 本Parked zing公司製）於自來水使其爲50g/l ，調製 成磷酸鹽化學表面處理液，於8 0 °C浸漬於該液3分鐘， 經水洗及純水洗，製作爲試驗板。 實施例3 將鹼脫脂處理液3加溫爲5 0 °C，在其中浸漬冷軋鋼 板1 2 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷酸 鹽化學表面處理液（註冊商品：Parbond-L3020曰本 Parkenzing公司製）於自來水使其爲50g/l ，調製成 磷酸鹽化學表面處理液，於4 3 °C浸漬於該液2分鐘，經 水洗及純水洗，製作爲試驗板。 (請先閱^^背面之注音筆項寫本頁) --裝 •訂- -•線- 本紙張尺度適用中國國家標雀（CN'ShVl規格（2.1〇 X 297公釐） -24- 508375 A7 ______ B7 五、發明說明έ2 ) 實施例4 --------------裝--- (請先閱讀背：注意事項^^寫本頁) 將驗脫脂處理液4加溫爲3 〇 °C，在其中浸漬兩面熔 融鍍鋅鋼板1 2 0秒鐘。其後不經水洗，溶解塗敷前之底 材用磷酸鹽化學表面處理液（註冊商品：parb〇nd-L 3020 曰本Parkenzing公司製）於自來水使其爲5 〇 g / 1 ，調 製成磷酸鹽化學表面處理液，於4 3 〇c浸漬於該液2分鐘 ’經水洗及純水洗，製作爲試驗板。 實施例5 -線· 將鹼脫脂處理液5加溫爲6 0 °C，在其中浸漬鋁-鎂 合金板6 0秒鐘。其後不經水洗，溶解5 0 g / 1塗敷前 之底材用磷酸鹽化學表面處理液（註冊商品：Parbond-L 3020日本Parkedzing公司製）及1 OOmg/1之HF於 自來水，調製成磷酸鹽化學表面處理液，於4 3 °C浸漬於 該液2分鐘，經水洗及純水洗，製作爲試驗板。 實施例6 經濟部智慧財產局員工消費合作社印製 將鹼脫脂處理液6加溫爲3 5 °C，於其中浸漬冷軋鋼 板1 8 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷酸 鹽化學表面處理液（註冊商品：Parbond-L 3020日本 Parker i zing公司製）於自來水使其爲5 0 g/Ι ，調製成 磷酸鹽化學表面處理液，於4 3 °C浸漬於該液2分鐘，經 水洗及純水洗，製作爲試驗板。 -25- 本紙張&度適闬中國國家標車（G\S)A4規格（210 X 297公釐） 508375 A7 經濟部智慧財產局員工消費合作社印制衣 _____B7_五、發明說明έ3 ) 實施例7 將鹼脫脂處理液5加溫爲4 0 °C，在其中浸漬冷軋鋼 板1 2 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷酸 鹽化學表面處理液（註冊商品：Parbond-L 3020曰本 Parkerizing公司製）於自來水使其爲5〇g/l ，調製成 磷酸鹽化學表面處理液，於4 3 °C浸漬於該液2分鐘，經 水洗及純水洗，製作爲試驗板。 實施例8 將鹼脫脂處理液1 2加溫爲5 0 °C，對於冷軋鋼板噴 霧9 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷酸鹽 化學表面處理液（註冊商品：Parbond-L 3150曰本 Parkenzmg公司製）於自來水使其爲45g/l ，調製成 磷酸鹽化學表面處理液，於4 0 °C浸漬於該液2分鐘，經 水洗及純水洗，製作爲試驗板。 實施例9 將鹼脫脂處理液1 3加溫爲4 0 t：，對於冷軋鋼板噴 霧9 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷酸鹽 化學表面處理液（註冊商品：Parbond_L 3020日本 Parkenzmg公司製）於自來水使其爲SQg/丨，調製成 磷酸鹽化學表面處理液，於4 〇 T：浸漬於該液2分鐘，經 水洗及純水洗，製作爲試驗板。 (請先閱讀背面之注意事項Η 裝--- 臂寫本頁) 訂· --線· 本紙張Κ度適用中國國家標進（CNS)A4規格（210x297公釐） -26- 508375 A7 B7 五、發明說明以 ) 比較例1 將鹼脫脂處理液7加溫爲4 5 °C，在其中浸漬冷軋鋼 板1 2 0秒鐘。其後不經水洗，溶解塑性加工潤滑前之底 材用磷酸鹽化學表面處理液（註冊商品：Parbond-181X日 本Parkenzmg公司製）於自來水使其爲90g/l ，調製 成憐酸鹽化學表面處理液，於8 0 °C浸漬於該液5分鐘， 經水洗及純水洗，製作爲試驗板。 比較例2 將鹼脫脂處理液8加溫爲3 5 °C，對於冷軋鋼板噴霧 1 2 0秒鐘。其後不經水洗，溶解塑性加工潤滑前之底材 用磷酸鹽化學表面處理液（註冊商品：parbond-421WD曰 本Parked zing公司製）於自來水使其爲50g/l ，調製 成磷酸鹽化學表面處理液，於8 0 t浸漬於該液5分鐘， 經水洗及純水洗，製作爲試驗板。 (請先閱讀背面之注意事項本頁) --裝 -訂· --線- 經濟部智慧財產局員工消費合作社印製 比較例3 將鹼脫脂處理液9加溫爲4 0 °C，於其中浸漬冷軋鋼 板1 2 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷酸 鹽化學表面處理液（註冊商品：Parbond_L3〇2〇曰本 Parkenzmg公司製）於自來水使其爲5〇g/i ，調製成 磷酸鹽化學表面處理液，於4 3 °C浸漬於該液2分鐘，經 水洗及純水洗^製作爲試驗板。 本紙張尺度適同中國國家標進（α\\)Α4規格（210 X 297公釐） -27- 508375 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明的 ) 比較例4 將鹼脫脂處理液1 0加溫爲3 0 °C，於其中浸漬兩面 熔融鍍鋅鋼板1 2 0秒鐘。其後不經水洗，溶解塗敷前之 底材用磷酸鹽化學表面處理液（註冊商品：ParboncU；L 3 020日本Parked zing公司製）於自來水使其爲5 〇 g / 1 ，調製成磷酸鹽化學表面處理液，於4 3 °C浸漬於該液2 分鐘，經水洗及純水洗，製作爲試驗板。 比較例5 將鹼脫脂處理液1 0加溫爲6 0 °C，在其中浸漬銘-鎂鋼合金板1 2 0秒鐘。其後不經水洗，溶解5 0 g / 1 塗敷前之底材用磷酸鹽化學表面處理液（註冊商品： Parbond-L 3020 日本 Parkerizing 公司製）及 1 〇 〇 m g / 1之H F於自來水，調製成磷酸鹽化學表面處理液，於4 3 t：浸漬於該液2分鐘，經水洗及純水洗，製作爲試驗板 〇 比較例6 將鹼脫脂處理液1 1加溫爲4 0 °C，於其中浸漬冷軋 鋼板1 2 0秒鐘。其後不經水洗，溶解塗敷前之底材用磷 酸鹽化學表面處理液（註冊商品：Parbond-L 3020曰本 Parkenzmg公司製）於自來水使其爲50g/l ，調製成 磷酸鹽化學表面處理液，於4 3 °C浸漬於該液2分鐘，經 水洗及純水洗，製作爲試驗板。 (請先間讀背面之注意事項1 裝--- ^寫本頁) -訂· ••線- 本紙張瓦度適用中國國家標舉（CI\’S)A4規格（210 X 297公釐） -28- 508375 A7 B7 五、發明說明鉍） 表3中示實施例，表4中示比較例中之化學表面處理 被膜之特性。 由其結果可確認採用本發明之鹼脫脂處理液，及脫脂 與化學表面處理方法的實施例1〜7係各種金屬材料均可 獲得優異之脫脂性及磷酸鹽化學表面處理性。又，含有表 面調整劑之實施例3、7係顯示不會有阻礙表面調整效果 ，確認還可兼具脫脂效果與表面調整效果的兩種性能。 與之相比，不含有鹼金屬鹽或銨鹽之比較例1，使用 聚氧化乙烯烷基醚之濃度低於本發明之下限的比較例2係 無法獲得充分之脫脂效果，無法得到均勻之磷酸鹽化學表 面處理被膜。聚氧化乙烯烷基醚之H L B在範圍外之比較 例3，聚氧化乙烯烷基醚之配合量超出上限，表面調整成 份濃度低之比較例4及5，使用聚氧化乙烯壬基苯醚之比 較例6，其被膜外觀都不均勻。 (請先閱讀背面之注意事項Η 裝—— 臂寫本頁) -訂. -線· 經濟部智慧財產局員工消費合作社印製 -29- 本紙張尺度適用中國國家標準（CNSM4規格（210 X 297公釐） 508375 A7 Β7 五、發明說明扣） 經濟部智慧財產局員工消費合作社印製 cn fe 錄 劍*N匣 04 S Cxfl VO CN 〇 〇 ε $ csl 〇 〇 r·"·" i 舞〇〇 n Csl IS 怎 錄㈣ m η m ε -^ hi) Ο CNl 〇 〇 ε $ CO 〇 〇 ν' 4 辑> un 剡 w旺 rs ε 〇J〇 CO CO 〇 〇 ε CNl 〇 〇 1 i 孽 S \〇 繇㈣ 劍忉匣 rsi ε — bJO v〇 Cs! 〇 〇 ε CO 〇 〇 r—Η W un 6 &J0 Γ"1 " ^ CN 〇 〇 ε $ CNI 〇 〇 r—Η 匡 ㈣寸 寸 燄働 劍 W匣 ε w) O cn 〇 〇 S 寸 沴 Ο Ο r—Η n cn 錄㈣ 劍N旺 ΓΜ ε — bD CO CN 〇 〇 ε οα 疹 Ο Ο r—H CNI 辑 n CNl 运鹯働 m m ^ ^ 劉Η接担 CM 6 OO 〇 〇 ε $ ο CN 沴 Ο Ο r i _ — K τ·丨…Η 劉H i妄怎 rs ε OX) o f i 〇 〇 ε Csl 疹 Ο Ο .......4 嫠 rrn 1 勁 猶 迦 an 驾 m if濺 勸 m m 羧1 画 _ tlmil Pt| .m m a M 紫 ㈣ 騷 ΠΠ mi 1 勁 m賴 胆鍅 m m m m a (請先閱讀背面之注意事項Η 裝—— π寫本頁) —“訂 ,線· 本紙張&度適用中國國家標準（CNS)A、1規格（210 x 297公釐） -30- 508375 B7 五、發明說明鉍) 表 4 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 鹼脫脂處理 液 7 8 9 10 10 11 磷酸鹽化學 塑性加 塑性加 塗敷前 塗敷前 塗敷前 塗敷前 表面處理用 工潤滑 工潤滑 之底材 之底材 之底材 之底材 途 前之底 材用 前之底 材用 用 用 用 用 被膜重量 3 . Og/m2 2.Og/m2 3.Og/m2 5.5g/m2 1.3 g/m2 3.5g/m2 底板被覆性 △ X Δ X X X 目視外觀 Δ X X X X Δ 化學表面處 理被膜之粒 徑 60 β m 60 β m 15 // m 20 β m 1 0 // m 15 # m 脫脂後之水 濕潤性 50% 0% 90% 100% 100% 20% --------------裝--- (請先閒讀背面之注咅？事項寫本頁) . --線· 經濟部智慧財產局員工消費合作社印製 〔發明之效果〕 本發明之金屬材料的鹼金屬脫脂處理液，及使用其脫 脂及化學表面處理方法係可以省去以往鹼脫脂步驟與磷酸 鹽化學表面處理步驟間必須且不可缺的水洗步驟，係一種 極具創意之革新技術。又，爲形成塗敷前底材面而施予磷 酸鹽化學表面處理時，若採用本發明則可以同時進行一般 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 508375 A7 _____B7__ 五、發明說明έ9 ) 所施行之表面調整處理與鹼脫脂處理，極爲有利。 又，本發明中所用界面活性劑具生物分解性，環保上 亦極優。 使用本發明技術可以期待縮短處理步驟，省去佔有空 間，提高生產效率，降低廢水處理上負擔等，極爲有利。 (請先閱讀背面之注意事項1 裝—— ¥寫本頁) -訂· 經濟部智慧財產局員工消費合作社印製 -32- 本紙張又度適用中國國家標準（CNS)A4規格（210 X 297公釐）ΗPage I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 to 3 g / 1. The p 碱 of alkali metal salt or liquid must be adjusted. Furthermore, it is advisable to completely omit alkaline dehydration of 1 to 13 degrees, or the total alkalinity is 1 degree or less, the pH is 13 or more, or the stability of the total solution entering the phosphate chemical surface treatment solution is not suitable. In terms of the concentration of the alkaline degreasing ammonium salt referred to herein, the present invention is adjusted to 8 to 13, and the total alkalinity is 2 to 10 degrees when the water washing step is followed by the fat step. When P is not satisfactory, when the alkalinity is above 15 degrees, if the surface treatment solution will hinder the smooth progress of phosphate on the phosphate degreasing place, the alkalinity at 1 to 15 degrees is based on 碱. 8 or less. In addition, the alkali degreasing treatment reacts on the chemical surface. The total alkalinity of the treated liquid refers to taking 10 m 1 of alkali de-threading. The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 10- 508375 Α7 Β7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Agricultural Co., Ltd. 5. Description of invention 6) Fat treatment solution, adding bromophenate blue as indicator, neutralization titration with 0. 1 N sulfuric acid aqueous solution, from blue The number of m 1 of the titrant required until it turns yellow is expressed. For example, a total alkalinity of 1 degree means that the above m 1 number is 1 m 1. As the third component of the alkaline degreasing treatment liquid of the present invention, pure water, deionized water, tap water, or the like can be used. After alkali degreasing, when forming a phosphate chemical surface treatment film for coating a substrate, it is preferable to uniformly deposit a film having a weight of about 2 to 5 g / m2, and a dense thin film phosphate film is preferable. For this reason, in the past, after alkali degreasing, surface conditioning treatment with a surface conditioner was performed, and then a phosphate chemical surface treatment for coating the substrate was performed. With surface and surface modifiers, both the effects of degreasing and surface adjustment can be met. The surface modifier can be at least one kind of phosphate particles of divalent or trivalent metal ions, and the particle diameter is 5 // m or less. Here, the divalent or trivalent metal ion is at least one selected from the group consisting of zinc ion (Z η 2 +), nickel (II) ion (Ni2 +), hafnium (II) ion (Μη2 +), and cobalt (II) 'ion (Co2 + ), Iron (II) ion (Fe2 +), calcium ion (C a 2 +), aluminum ion (A 1 3 +), and iron (III) ion (F e 3+) are suitable. The phosphate of the divalent or trivalent metal ion can be specifically Zll3 (P04) 2, Zll2Fe (P04) 2, Z η 2 Ni (P04) 2, Ni3 (p.〇4) 2. Zn2Mη (P〇4) 2, Μη3 (ρ〇4) 2, Μ η 2 Fe (P〇4) 2, Ca3 (p〇4) 2, (please read the precautions on the back of this page) Binding, i-line · This paper size applies to China National Standards (CNS) Al specification C210 X 297 public love) -11-508375 Printed by A7 B7____, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention since) ζ η 2 C a (P04) 2, C03 (P04) 2, A1P04, F e PO 4 and the like. These may also be hydrates. In addition, the lower limit of the particle size is not particularly limited, but it is preferable to be smaller. However, considering technical aspects of manufacturing, ease of acquisition, and other practically available considerations, it is preferably about 0.1 / m. Surface modifiers can also be titanium colloids. In the alkali degreasing treatment liquid of the present invention, when the concentration of the surface conditioner is at least one kind of divalent or trivalent metal ion phosphate, it must be 0 · 01 ~ 30 g / l, and 0 · 0 3 ~ 2 〇g / l is suitable, and 0. 05 ~ 1 0 g / 1 is more preferable, and the best system is 0. 1 ~ 1 0 g / 1. For titanium colloid, it must be 0 · 0 0 1 ~ 5 g / 1 'is preferably from 0.05 to 3 g / l, and more preferably from 0.05 to 3 g / l. When the concentration of each surface adjusting agent is lower than the above-mentioned lower limit 値, the surface adjusting effect cannot be obtained, and a uniform and dense phosphate chemical surface treatment film cannot be obtained. In addition, if the surface conditioner exceeds the above-mentioned upper limit concentration, the surface adjustment effect is saturated when the metal material is brought into contact with the degreasing treatment liquid containing the surface conditioner, so it is not economical. The surface of the polyoxyethylene alkyl ether-based metal material in the alkali degreasing treatment liquid used in the present invention has a weak adsorption force, so when used with a surface modifier, components that have a surface adjustment effect from the finished degreased part are adsorbed and displayed. Outstanding surface adjustment effect. In addition, the alkali degreasing treatment system of the present invention may contain a supplementary additive for improving the cleaning effect in addition to the above-mentioned components. It can contain, for example, cation components (Co2 +, Mg2 +, etc.) that can be clamped in industrial water, or dissolve to (please read the precautions on ti # side first-I. This page IT: | line · This paper size applies China National Standard (CNS) Al Specification (210 X 297 mm) -12- 508375 A7 B7 V. Description of Invention 60) The component of the processed metal material in the alkaline degreasing treatment solution printed by the employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ( Z n2 +, A 1 3 +, etc.) amine carboxylic acid type, hydroxy carboxylic acid type, phosphonic acid type clamping agent (for example, ethylene diamine tetraacetate (sodium salt, etc.), citrate (sodium salt, etc.) , Glutarate (sodium salt, etc.), 2-phosphonic acid butanetricarboxylic acid 1, 2, 4, etc.), or can prevent the oil once removed by the surfactant from adhering to the metal material to be treated Also suitable are cellulose derivatives such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxybutyl methyl cellulose. When using these supplementary additives, it must be used in a concentration range that does not cause problems when mixed into the subsequent phosphate chemical surface treatment solution. However, if it can be formed into a normal phosphate coating film ', the blending amount is not limited. Generally, the concentration of the clamping agent in the alkali degreasing treatment liquid of the present invention is preferably 1 g / 1 or less, and more preferably 0.01 to 1 g / 1, which is considered to be mixed in the subsequent phosphate chemical surface treatment liquid. In the case of problems, 0 · 01 ~ 0.5 g / l is more suitable, and the concentration of cellulose derivative is preferably 3 g / 1 or less, and more preferably 〇1 ~ 3 g / 1, and it may be mixed into the latter. For problems in phosphate chemical surface treatment fluid, it is more preferable to use 0.01 ~ lg / 丨. In general, in order to suppress problems caused by foaming during cleaning operations, the degreasing agent is contained in the alkaline degreasing treatment solution, and the defoaming agent may be contained in the alkali degreasing treatment solution of the present invention. This antifoaming agent can be appropriately selected and used from a general user. The alkali degreasing treatment liquid of the present invention is made of HLB12 ~ 17 polyoxyethylene storage ether, at least one metal test salt and money salt, and a surface conditioner (at least one divalent or trivalent metal ion Phosphate particles with a particle size of 5 // m or less or titanium colloids), and condensed phosphoric acid alkali salts, silicic acid alkali salts, supplementary additives, antifoaming agents, etc., when used or dissolved (please read the bee first ^^ Note on this page) — Binding — Binding — — Thread-This paper has been passed through the Ningguo State Standard (21〇X 297 public love) 13- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 508375 A7 B? 5. Description of the invention 6ι) Dispersed in water, it can be prepared. It can be mixed by stirring with a blade. In addition, the adjustment of the total alkalinity and pH can be performed using sodium hydroxide, ammonia, phosphoric acid, sulfuric acid, and the like as necessary. The alkali degreasing treatment liquid of the present invention can be used for degreasing metal materials to which oil has adhered. The metal materials to which phosphate treatment is usually applied adhere to the oil used in the previous steps such as extrusion, cutting and the like. Specifically, the attached oil is engine oil, kerosene, light oil, cutting oil, turbine oil, rust-proof oil, extrusion oil, spindle oil, and the like. The amount of oil adhered is not particularly limited. In addition, iron powder or other dirt mixed with the oil may be attached thereto. The kind of metal material to which the alkali degreasing treatment liquid of the present invention is applied is not particularly limited, and can be various steel materials such as steel plates (cold rolled steel plates, hot rolled steel plates, etc.). Galvanized steel (fused galvanized steel, galvanized steel, galvanized steel containing aluminum as an alloy), and various aluminum materials, such as aluminum plates and aluminum alloys (JIS 2000 (Al-Cu-Mg), 5000 (A1-Mg) and 6000 (A1-Mg — S i) alloys, etc.). The shape of the metal material is also not particularly limited. The alkali degreasing treatment liquid of the present invention is sprayed or immersed for 30 to 600 seconds at a temperature of 30 to 70 ° C, and is suitable for the surface of metal materials with oil. After the degreasing treatment (in this degreasing treatment, it is possible to combine the surface adjustment point as described above) with a phosphate chemical surface treatment without washing, so that the characteristics of the alkali degreasing treatment liquid of the present invention can be brought into full play. However, instead of the alkaline degreasing treatment liquid used in the previous alkaline degreasing treatment, this paper & degree suitable for the Chinese national standard (CNSM4 specification (210 X 297 mm)) -14- ----------- --- Packing --- (please read the general note of the first? Matters write this page), order: —line- 508375 A7 B7 V. Description of the invention 62) Mingzhi alkaline degreasing treatment liquid is not a problem. That is to say, the alkaline degreasing treatment solution of the present invention can be used for alkaline degreasing, water washing, and then phosphate chemical surface treatment, or alkaline degreasing, water washing, and surface adjustment treatment can be applied, and then phosphate chemical surface treatment can be performed without water washing. . The present invention is also a method for using the alkali degreasing treatment liquid of the present invention, that is, after contacting a metal material with the alkali degreasing treatment solution of the present invention, it is contacted with a phosphate chemical surface treatment solution without water washing to form phosphate Degreasing and chemical surface treatment method for metal materials characterized by chemical surface treatment film. The conditions for contacting the metal material with the alkali degreasing treatment liquid are as described above. In the present invention, after the alkali degreasing treatment, the phosphate chemical surface treatment can be applied without washing with water. Phosphate chemical surface treatment can be carried out with commonly known or commonly used phosphate chemical surface treatment liquids and treatment conditions (chemical surface treatment conditions). Whether it is all known or commonly used, here is an example. The phosphate chemical surface treatment liquid used in the method of the present invention is a zinc phosphate chemical surface treatment liquid, and moreover, it basically contains 0.5 to 20 g / l zinc ion, 10 to 50 g / l phosphate ion and water, and the free acidity is 0.5. 5 ~ 15 ° C zinc phosphate chemical surface treatment solution is suitable. More specifically, when used for a coating substrate, the phosphate chemical surface treatment liquid contains 0.5 to 5 g / l zinc ion, 10 to 20 g / 1 phosphate ion, and water based on the required film weight. The free acidity is preferably 0.5 to 4.0 degrees. When it is used for a lubricating substrate or an anti-rust coating, the phosphate chemical surface treatment solution contains 5 to 20 g / zin from the weight of the required coating. (Please read the precautionary notes on this page first to write this page) Binding, ordering: Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (0 X 297 mm) -15- 7 3 8ο A7 __; __ B7__ V. Description of the invention 纟 3) ions, 10 ~ 50g / l phosphate ion and water, free acidity 4.0 ~ 15 degrees, especially 5.0 ~ 13 degrees. Here, the supply source of zinc ion may be a zinc compound soluble in an aqueous phosphoric acid solution, such as zinc oxide, zinc phosphate, zinc nitrate, etc., and the supply source of phosphate ion may be phosphoric acid (orthophosphoric acid). The above-mentioned free acidity is difficult to be measured with a p Η tester (glass electrode) when it is necessary to measure a low p 2 of about 2 to 3 with excellent reproducibility, so this is the acidity of the phosphate chemical surface treatment liquid. Degree, instead of ρ Η, substitute 値 for general use, to take 10 m 1 phosphate chemical surface treatment solution, take bromophenol blue as the indicator, neutralize and titrate with 0.1 N sodium hydroxide aqueous solution, change from yellow to The number of m 1 of the titration solution required until blue, for example, 1 degree of free acidity means that the number of m 1 is 1 m 1. The phosphate chemical surface treatment liquid used in the method of the present invention may contain a chemical surface treatment accelerator to improve the etching force of acid and promote the chemical surface treatment reaction when used in any of the above applications, to destroy the oxide film on the metal surface to assist the etching. Etching aid for the reaction, to improve the adhesion of the film or other metal ions used to improve the chemical stability to acids and alkalis. Chemical surface treatment accelerators can be nitrite ions (supplied as sodium nitrite, etc.), hydroxyammonium ions (supplied as hydroxyammonium sulfate, etc.), chlorate ions (supplied as sodium chlorate, etc.), and nitrobenzenesulfonic acid ions ( Provided by sodium nitrobenzene sulfonate, etc.), hydrogen peroxide, organic peroxides (e.g. ethyl hydrogen peroxide, isopropyl hydrogen peroxide, etc.), as shown in JP-A-8-302 0 47 )Wait. The chemical surface treatment accelerator is usually preferably contained at a concentration of 0.05 to 2.0 g / 1. (Please read the precautionary note of the noodles first --- install --- write this page) -Line · Printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper is compliant with China National Standard (CNS) A4 (210 X 297 mm) -16- Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 508375 A7 B7 V. Description of the invention 纟 4) Uranium engraving aids include fluoride ions, silicon fluoride ions, etc. These can be contained in phosphate chemical surface treatment liquid as sodium salt, ammonium salt or free acid (hydrofluoric acid, silicon hydrofluoric acid, etc.). The concentration of the uranium engraving aid when contained is preferably from 0.1 to 2.0 g / l. Other metal ions can use nickel ions (Nι2 +), copper ions (Cu2 +), cobalt ions (C2 +), etc., which can mainly improve the adhesion of the film, and / or mainly improve the chemical stability of the film (acid resistance, acid resistance Basic) manganese ions (Mn2 +), magnesium ions (Mg2 +), calcium ions (C a 2+), etc. These can be used as nitrates and phosphates in phosphate chemical surface treatment fluids. When the other metal ion is contained, the concentration is 5 to 50 mg / l when the copper ion is contained, and the other metal ion is preferably 0.1 to 3.0 g / 1. The method for preparing the phosphate chemical surface treatment liquid used in the method of the present invention is not particularly limited. Generally, only a phosphate ion supply source, a zinc ion supply source, and a chemical surface treatment accelerator, an etching aid, and / or the like as required A metal ion supply source can be prepared by dissolving it in water to a predetermined concentration. The prepared phosphate chemical surface treatment liquid is suitable for metal materials treated by the alkali degreasing treatment liquid of the present invention without washing with water. When the phosphate chemical surface treatment liquid is used to treat a metal material, the treatment method is preferably a spray treatment or a dipping treatment. The processing temperature, processing time and film weight at this time vary depending on the application of the film. The phosphate chemical surface treatment liquid is used to form a coated substrate, and the paper is suitable for Chinese papers (CNS) A4 (210 X 297 mm) ---------- ---- Equipment --- (Please read the note on the back? Matters to write on this page), order ·-· line. 508375 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention 65) Film In this case, it is better to deposit a thin film type uniform and dense zinc phosphate film with a film weight of about 2 to 5 g / m2. The temperature of the treatment liquid at the time of burial is preferably 35 to 60 ° C, and the treatment time is preferably 30 seconds to 10 minutes. When the phosphate chemical surface treatment liquid is used to form a film for a lubricating substrate, it is preferable to deposit a thick film type zinc phosphate film having a film weight of about 5 to 20 g / m2. The temperature of the processing liquid during processing is preferably 60 to 9 Ot, and the processing time is preferably 30 seconds to 10 minutes. By adopting the degreasing and chemical surface treatment method of the present invention, a phosphate chemistry having the same appearance and performance as the phosphate chemical surface treatment film obtained in a series of steps of conventional degreasing-washing- (surface adjustment) -chemical surface treatment- can be obtained. Surface treatment coating. After the phosphate chemical surface treatment, in order to remove the adhering phosphate chemical surface treatment liquid, the metal materials are washed here with water or hot water. After that, if necessary, it should be dried. If it is to be applied, it should be applied with a coating treatment. For lubrication purpose, a reactive soap treatment or solid lubricant should be applied. For the purpose of rust prevention, it is usually used directly after drying or coated with rust preventive oil. Next, practical examples and comparative examples are shown to specifically explain the effects of the present invention. In addition, the examples are only examples of the application of the present invention, and there is no restriction on the application and the raw materials of the present invention. 1 · The test materials are cold-rolled steel plates (0.8mm thickness, SPCC-SD), and both sides are hot-dip galvanized steel plates (registered trademarks ·· Silver Alloy, made in Japan). (Please read the precautions for the surface first. (In this page) Γ Good paper size is applicable to China National Standards (CNSM.! Specifications (210 x 297 g t) -18- 508375 A7 ____ B7 ^ _ _ _ V. Description of the invention 66) Made by iron company, plate thickness: 0 8mm, galvanized adhesion amount: 45 g / m2 on one side), aluminum-magnesium alloy plate (plate thickness: 1.0 mm, JI SA 5 0 5 2), and the following examples and comparative examples were treated. In addition, each test material was coated with 2 g / m 2 of commercially available clean rust preventive oil (registered trademark: Ν Ο X RUST 530 — 40, manufactured by Parker Kosan Co., Ltd.), and 100 coated oil plates were stacked on top of each other. Set, tighten with a torque wrench with a torque pressure of 70Kg f / Cm, and place it in a humid box with a relative humidity of more than 95% at 60 ° C for 4 days before using it. The compositions of the alkaline degreasing treatment liquids used in the examples and comparative examples are shown in Tables 1 and 2. The water system constituting the degreasing treatment liquid is omitted in Tables 1 and 2, but the water system uses tap water. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-19- This paper size applies to the Chinese National Standard Vehicle (CNS) A4 specification (210 X 297 mm) 508375 V. Description of Invention 67 Alkali-based degreasing treatment solution 6 Polyoxyethylene alkyl ether 7g / l 16.6 VO Nl2HP〇4 12 degrees CS1 ON * 2 Brebalen ZN in terms of titanium is o.lg / lm S5 ^ advise 5g / l 16.6 un N a 2 C 0 3 (NH4) 2S〇4 cn 10.3 Zn3 (P〇4) 2 • 4H2〇ε cn lg / 1 mm ^ mm Scratch lg / 1 14.3 oo N a 2 C 〇3 Na2〇-Si〇2 side r— CN r—Η r · Η Zn2Fe9P〇4) 2 • 4H2〇ε $ un 2g / l Alkaline degreasing treatment solution 3 2g / l 14.3 o Na2HP〇4 NaN〇2 side CS OO Zn2Fe (P〇4) 2 • 4H2. ε $ i " 1 i 5g / lmm ^ mm 鎏 to 7g / l cn inch r " 1 io N a3P〇4 (NH4) 2S〇4 m un CN t—H 1 1 1 alkaline degreasing treatment liquid 1 2g / l cn csi 1—H oo Na3P〇4 Na4P2〇7 10 degrees CNl 1 1 1 Species concentration HLB E〇 Additional Moire number Species Total alkalinity pH 値 Species particle size * i Concentration interface activity m Surface adjustment component (Μίί? < 4㈤.szpssd 柃 ΕΠ: post light duty_) NZ ui qePQ: * 轵 震 (fM ^ ebismuth ti ®: 026 — V Ί) Tantalum: 1 * -------------- install --- (Please read the precautions on the back and write this page first), order · .line · This paper size applies to China National Standards (CNS ) A4 specification (210 X 297 mm) -20- 508375 A7 B7 V. Description of invention 68) ei_i 6 issued persuasion 0 mss Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 8 faer I ΐ®_ίοί® CSII mb纒 m 1 i DJQ r—Η τ—Η ν〇ι—Η 〇Ph rs οΰ z cn ο ON C < υ σ3 X) (D one! Zn PQ Γ: 〇, Ν3 * Hull g — ^ ¢ 1 c〇K] ι 4, ^ bi) inch m inch, _ ΟΟ • rr 〇cu ΓΟ o3 z marriage ο f Η, · Η OJ 〇 Ρη 〇U Κ ^ CSI CS C! Ν · ε τ—Η, Μ Ο ι ... 4 K] age τ—Η '^. 0D τ—Η inch r—Η CN τ-Η 〇 ^ 00 〇A 姻 ΓΠ Ο r—Η γμ 6 9 Two inches c N · ε m 1 < tO) r—Η rs / m \ rs 〇 rO CN / -— N 〇 r \ a ι, DJQ bJO Ο inch ΟΟ 5 ί side, " Η t-M 〇 crv rs to Ο ι < ^ Η uo rs 〇4 τ—Η ^ hC fN Ο ο c3 c3 zz fH N · Μ CN 〇g fi ΟΟ ο E Ν3 oa cd z CN c N · Ilf τ 4 cn inch ο ι 1 < ΓΝ o side CO τ—Η 1 1 1 Ο τ—Η r—Η 55 ί 4 bi) cn CN Ο Ο θ ′ 1 1 1 Csl r—Η 1 ο 5 gong side one * Sao side: PQ Λ i ^ I Mgs Step 1® M ^! \ Ts 顾 制 \ lml1 P _ η-I κ Sm \ 1mi1 P cloud κ Ρ. Ornil P Μ «虼 K 萌 蘅 馨 蘅 陌 鼷 _chain Φ ----- --------- Installation— (Please read the note page of the top page first) • Order: -1 line · This paper size applies to China National Standard (CN'S) A4 specification (210x297 mm) 508375 Α7 V. Description of the invention (19) 2. Evaluation test method 2.1 Film weight First, the weight of the treated board after chemical surface treatment (expressed as W 1 [g]) is measured, and then the following stripping solution is used to strip the chemical surface. The treatment board is subjected to film peeling. After treatment, the weight (expressed as w 2 [g]) is measured, and the film weight is calculated using formula (1). Film weight [g / m2] = (W1-W2) / surface area of the treated product peeling solution, peeling conditions (1) peeling solution when cold-rolled steel sheet: 5 wt% chromic acid aqueous solution peeling condition: 75 ° C, 15 minutes Dipping and peeling (2) Stripping solution on both sides of hot-dip galvanized steel sheet: 2% by weight of ammonium dichromate + 28% ammonia water + 49% by weight of water Stripping conditions: Normal temperature, 15 minutes by peeling and peeling (3) Aluminum-magnesium alloy sheet Liquid: 5% by weight chromic acid aqueous solution Peeling conditions: 15 minutes at room temperature, dipping and peeling 2.2 Coverability of the bottom plate Using a scanning electron microscope (SEM), the crystals of the deposited film were enlarged and observed at a magnification of 150 times. Based on the following criteria, the scale of the paper has been expanded since then. The paper size is applicable to the Chinese National Standard Vehicle (CNS) A4 (210 X 297 mm). Please read the precautions on the back page. Printed by the cooperative -22- 508375 A7 Printed clothing B7 by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs_5. Invention descriptions such as) Coverability of the sheet metal (with or without the bottom plate exposed) ° The evaluation standard does not expose the bottom plate at all—0 (Good) Slightly Exposed bottom plate-△ (slightly poor) The bottom plate is completely exposed-x (extremely poor) 2.3 Visual Appearance The appearance after chemical surface treatment was evaluated according to the following criteria. Finished products with uniform evaluation criteria, no uneven or poor chemical surface treatment — 0 (good) slightly uneven or defective chemical surface treatment — △ (slightly worse) There are uneven or defective chemical surface treatments overall Where — x (very poor) The crystal particle size of the 2 · 4 chemical surface treatment liquid coating was obtained by expanding the SE M to a factor of 1,500. 2.5 Degreasing properties of alkaline degreasing solution Contact the test material with the alkaline degreasing treatment solution at a predetermined temperature for a predetermined time (the same conditions as in the examples and comparative examples described later), and immediately wash with water (spray for 30 seconds), vertical After standing for 1 minute, the water-wet area occupied was visually observed, and the degreasing property was evaluated. (Please read the notes on the back first to write this page) Binding ·-Thread _ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm-23- 508375 A7 B7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative V. Description of the invention) Example 1 The alkali degreasing treatment liquid 1 was heated to 45 ° C, and the cold-rolled steel sheet was immersed therein for 120 seconds. After that, the substrate before being plastic-lubricated was dissolved without washing with water. A phosphate chemical surface treatment liquid (registered product: parbond-181X manufactured by Parkenzing, Japan) was used in tap water to make 90 g / l to prepare phosphate. The chemical surface treatment liquid was immersed in the liquid at 80 ° C for 5 minutes, and washed with water and pure water to prepare a test plate. Example 2 The alkali degreasing treatment liquid 2 was heated to 35 ° C, and sprayed on a cold-rolled steel sheet for 120 seconds. After that, the substrate before being plastic-lubricated was dissolved without washing with water. A phosphate chemical surface treatment liquid (registered product: parbond-421WD manufactured by Parked Zing Co., Ltd.) was tap water to make it 50 g / l to prepare a phosphate chemical surface. The treatment solution was immersed in the solution at 80 ° C for 3 minutes, and washed with water and pure water to prepare a test plate. Example 3 The alkali degreasing treatment liquid 3 was heated to 50 ° C, and a cold-rolled steel sheet was immersed therein for 120 seconds. After that, the substrate before coating was dissolved without washing with a phosphate chemical surface treatment liquid (registered product: Parbond-L3020, manufactured by Parkenzing Co., Ltd.) in tap water to 50g / l to prepare a phosphate chemical surface treatment liquid. , Immersed in the solution at 4 3 ° C for 2 minutes, and washed with water and pure water to make a test plate. (Please read the Zhuyin pen entry on the back of ^^ first to write this page)-Binding • Binding — — • Thread-This paper size applies to China's national standard bird (CN'ShVl specification (2.1〇X 297 mm) -24- 508375 A7 ______ B7 V. Description of the invention 2) Example 4 -------------- Installing --- (Please read the back first: Precautions ^^ Write this page) Degreasing treatment liquid 4 The heating was performed at 30 ° C, and both sides of the hot-dip galvanized steel sheet were immersed therein for 120 seconds. After that, the substrate before coating was dissolved in water with a phosphate chemical surface treatment solution (registered product: parb〇nd-L 3020, manufactured by Parkenzing) without being washed with water to make it 50 g / 1 in tap water to prepare phosphoric acid. The salt chemical surface treatment solution was immersed in the solution for 2 minutes at 430 ° C, and washed with water and pure water to prepare a test plate. Example 5-Wire · The alkaline degreasing treatment liquid 5 was heated to 60 ° C, and an aluminum-magnesium alloy plate was immersed therein for 60 seconds. After that, 50 g / 1 of a phosphate chemical surface treatment liquid (registered product: Parbond-L 3020 manufactured by Parkedzing, Japan) and a 100 mg / 1 HF in tap water were dissolved in water without dissolving 50 g / 1 before coating. Phosphate chemical surface treatment liquid, immersed in the liquid at 4 3 ° C for 2 minutes, washed with water and pure water to make a test plate. Example 6 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The alkali degreasing treatment liquid 6 was heated to 35 ° C, and a cold-rolled steel plate was immersed therein for 180 seconds. After that, the substrate before coating was dissolved without washing with a phosphate chemical surface treatment solution (registered product: Parbond-L 3020 manufactured by Japan Parker Izing Co., Ltd.) in tap water to make it 50 g / 1 to prepare phosphate. The chemical surface treatment solution was immersed in the solution at 4 3 ° C for 2 minutes, and washed with water and pure water to prepare a test plate. -25- This paper is suitable for China National Standard Car (G \ S) A4 size (210 X 297 mm) 508375 A7 Printed clothing for the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _____B7_V. Invention Description 3) Example 7 The alkaline degreasing treatment solution 5 was heated to 40 ° C, and a cold-rolled steel sheet was immersed therein for 120 seconds. Thereafter, the substrate before coating was dissolved without washing with a phosphate chemical surface treatment solution (registered product: Parbond-L 3020, manufactured by Parkerizing Co., Ltd.) in tap water to make it 50 g / l to prepare a phosphate chemical. The surface treatment liquid was immersed in the liquid at 4 3 ° C for 2 minutes, and then washed with water and pure water to prepare a test plate. Example 8 The alkaline degreasing treatment solution 12 was heated to 50 ° C, and the cold-rolled steel sheet was sprayed with 90 seconds. After that, the substrate before coating was dissolved without washing with a phosphate chemical surface treatment solution (registered product: Parbond-L 3150, manufactured by Parkenzmg Co., Ltd.) in tap water to 45g / l to prepare a phosphate chemical surface treatment. The solution was immersed in the solution at 40 ° C for 2 minutes, and then washed with water and pure water to prepare a test plate. Example 9 The alkali degreasing treatment solution 13 was heated to 40 t: and sprayed on a cold-rolled steel sheet for 90 seconds. After that, the substrate before coating was dissolved with a phosphate chemical surface treatment liquid (registered product: Parbond_L 3020 manufactured by Parkenzmg Japan) without being washed with water. The tap water was made into SQg / 丨 to prepare a phosphate chemical surface treatment liquid. 〇T: immersed in the solution for 2 minutes, washed with water and pure water to make a test plate. (Please read the precautions on the back first. --- Arm write this page) Ordering ----Lines This paper κ degree applies to China National Standard (CNS) A4 specification (210x297 mm) -26- 508375 A7 B7 5 (Explanation of the invention) Comparative Example 1 The alkali degreasing treatment liquid 7 was heated to 45 ° C, and a cold-rolled steel sheet was immersed therein for 120 seconds. After that, the substrate before being plastic-lubricated was dissolved without washing with water. A phosphate chemical surface treatment liquid (registered product: Parbond-181X manufactured by Parkenzmg, Japan) was made into tap water at 90 g / l to prepare a phosphate salt chemical surface treatment. The solution was immersed in the solution at 80 ° C for 5 minutes, and then washed with water and pure water to prepare a test plate. Comparative Example 2 The alkali degreasing treatment liquid 8 was heated to 35 ° C, and sprayed on a cold-rolled steel sheet for 120 seconds. After that, the substrate before being plastic-lubricated was dissolved without washing with water. A phosphate chemical surface treatment liquid (registered product: parbond-421WD manufactured by Parked Zing Co., Ltd.) was tap water to make it 50 g / l to prepare a phosphate chemical surface. The treatment solution was immersed in the solution at 80 t for 5 minutes, and washed with water and pure water to prepare a test plate. (Please read the caution page on the back first)-Binding-binding--Line-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Comparative Example 3 Warm the alkaline degreasing treatment solution 9 to 40 ° C. The cold-rolled steel sheet was dipped for 120 seconds. After that, the substrate before coating was dissolved without washing with phosphate chemical surface treatment liquid (registered product: Parbond_L3202, manufactured by Parkenzmg Co., Ltd.) in tap water to make it 50g / i to prepare phosphate chemistry. The surface treatment liquid was immersed in the liquid at 4 3 ° C for 2 minutes, and then washed with water and pure water to prepare a test plate. The size of this paper is in line with China's national standard (α \\) A4 specification (210 X 297 mm) -27- 508375 A7 B7 (Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention) Comparative Example 4 Alkali The degreasing treatment solution was heated at 10 ° C to 30 ° C, and both sides of the galvanized steel sheet were immersed therein for 120 seconds. Thereafter, the substrate was coated with a phosphate chemical surface treatment liquid (registered product: ParboncU; L 3 020 manufactured by Parked Zing, Japan) without being washed with water in tap water to make it 50 g / 1 to prepare phosphate. The chemical surface treatment solution was immersed in the solution at 4 3 ° C for 2 minutes, and washed with water and pure water to prepare a test plate. Comparative Example 5 The alkaline degreasing treatment solution was heated to 60 ° C at 10 ° C, and the Ming-magnesium steel alloy plate was immersed therein for 120 seconds. After that, 50 g / 1 of the phosphate chemical surface treatment liquid (registered product: Parbond-L 3020 manufactured by Japan Parkerizing Co., Ltd.) and 100 mg / 1 of HF in tap water were dissolved without washing. Prepared as a phosphate chemical surface treatment solution at 4 3 t: immersed in the solution for 2 minutes, washed with water and pure water, and made into test plates. Comparative Example 6 The alkali degreasing treatment solution 11 was heated to 40 ° C. The cold-rolled steel sheet was immersed therein for 120 seconds. After that, the substrate before coating was dissolved without washing with a phosphate chemical surface treatment solution (registered product: Parbond-L 3020 manufactured by Parkenzmg Co., Ltd.) in tap water to 50g / l to prepare a phosphate chemical surface treatment. The solution was immersed in the solution at 4 3 ° C for 2 minutes, and then washed with water and pure water to prepare a test plate. (Please read the precautions on the back 1) --- ^ write this page)-Order · •• Line-The paper wattage is applicable to China National Standard (CI \ 'S) A4 specification (210 X 297 mm) -28-508375 A7 B7 V. Description of the invention Bismuth) Table 3 shows the examples, and Table 4 shows the characteristics of the chemical surface treatment film in the comparative example. From the results, it was confirmed that the various metal materials of Examples 1 to 7 using the alkali degreasing treatment liquid and the degreasing and chemical surface treatment method of the present invention can obtain excellent degreasing properties and phosphate chemical surface treatment properties. In addition, the examples 3 and 7 containing the surface-adjusting agent showed no effect of impeding the surface-adjusting effect, and it was confirmed that both performances of the degreasing effect and the surface-adjusting effect could be achieved. In contrast, in Comparative Example 1, which does not contain an alkali metal salt or ammonium salt, Comparative Example 2 using a polyoxyethylene alkyl ether having a concentration lower than the lower limit of the present invention cannot obtain a sufficient degreasing effect and cannot obtain a uniform phosphoric acid. Salt chemical surface treatment coating. Comparative Example 3 where the HLB of the polyoxyethylene alkyl ether is out of range, Comparative Examples 4 and 5 in which the blending amount of the polyoxyethylene alkyl ether exceeds the upper limit and the concentration of the surface adjustment component is low, and the comparison using the polyoxyethylene nonylphenyl ether In Example 6, the appearance of the coating was not uniform. (Please read the Precautions on the back of the book-Arm writing this page) -Order. -Line · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics-29- This paper size applies to Chinese national standards (CNSM4 specifications (210 X 297 (Mm) 508375 A7 Β7 V. Description of invention deduction) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy cn fe Recording Sword * N Box 04 S Cxfl VO CN 〇〇ε $ csl 〇〇r · " · " i dance 〇〇n Csl IS ㈣ m η m ε-^ hi) 〇 CNl 〇〇ε $ CO 〇〇ν '4th Series > un 剡 w 旺 rs ε 〇J〇CO CO 〇〇ε CNl 〇〇1 i SS \ 〇 繇 ㈣ Sword box rsi ε — bJO v〇Cs! 〇〇ε CO 〇〇r—Η W un 6 & J0 Γ " 1 " ^ CN 〇〇ε $ CNI 〇〇r—Η 匡㈣inch inch flame sword W box ε w) O cn 〇〇S inch 沴 〇 〇 r—Η n cn ㈣ N N N ΓΜ ε — bD CO CN 〇〇ε οα rash 〇 〇 r—H CNI series n CNl operation鹯 働 mm ^ ^ Liu Ye takes over CM 6 OO 〇〇ε $ ο CN 沴 Ο Ο ri _ — K τ · 丨 ... Η Liu H i rsr ε OX) ofi 〇〇ε Csl rash 〇 Ο ... ... .4 rnrrn 1 Jin Yujia an driving m if splash persuade mm carboxyl 1 painting _ tlmil Pt | .mma M ㈣ 骚 sao ΠΠ mi 1 Jin m Lai dan bile 鍅 mmmma (Please read the precautions on the back first. Installation-π (Write this page) — "Order, line · This paper & degree applies to Chinese National Standard (CNS) A, 1 specifications (210 x 297 mm) -30-508375 B7 V. Description of the invention Bismuth) Table 4 Comparative Example 1 Comparison Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Alkali degreasing treatment liquid 7 8 9 10 10 11 Phosphate chemical plasticity plus plasticity before coating Before coating Before coating Substrate Substrate Substrate Substrate Before substrate Substrate Before substrate Substrate film Weight 3. Og / m2 2. Og / m2 3. Og / m2 5.5g / m2 1.3 g / m2 3.5g / m2 Floor coating △ X Δ XXX Visual appearance Δ XXXX Δ Particle size of chemical surface treatment film 60 β m 60 β m 15 // m 20 β m 1 0 // m 15 # m Wet water after degreasing 50% 0% 90% 100% 100% 20% -------------- install --- (please read the note on the back first? (Please write this page).-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Effects of the Invention] The alkali metal degreasing treatment solution for the metallic materials of the present invention and the degreasing and chemical surface treatment methods can be omitted. The necessary and indispensable water washing step between the alkaline degreasing step and the phosphate chemical surface treatment step in the past is a very innovative and innovative technology. In addition, when the phosphate chemical surface treatment is applied to form the surface of the substrate before coating, if the present invention is adopted, the general paper size can be simultaneously applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 508375 A7 _____B7__ V. Description of the invention 9) The surface adjustment treatment and alkali degreasing treatment performed are extremely advantageous. In addition, the surfactant used in the present invention is biodegradable and excellent in environmental protection. Using the technology of the present invention can be expected to shorten the processing steps, save the occupied space, improve production efficiency, reduce the burden on wastewater treatment, etc., which is extremely advantageous. (Please read the note on the back 1 Pack-¥ write this page) -Ordered · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-32- This paper is also applicable to China National Standard (CNS) A4 (210 X 297) Mm)