201107531 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種金屬表面處理液以及使用該處理液 之金屬表面處理方法，而該處理液係用以對金屬材料於同 一步驟中進行表面淨化處理（脫脂）與底塗處理 (Pretreatment of Painting)的處理液。 【先前技術】 在對金屬材料進行塗裝時，作為提高塗膜密著性與塗 裝後耐蝕性之目的，通常是在塗裝前施行底塗處理的。特 別是在以沖壓（stamping)或熔接而形成具有複雜形狀之鈑 金構造體時，則廣泛地使用電解著色分佈力（throwing power of electrolytic colouring)良好的化成處理型之 底塗處理，例如磷酸鋅系化成處理或鍅系化成處理等。底 塗處理之一般的處理步驟係有（1)脫脂-(2)水洗-(3)底塗 處理-(4)水洗-(5)乾燥，（2)與（4)之水洗步驟可依需要而 多段進行，亦可作成熱水洗滌。更且，（5)之乾燥步驟如持 續塗裝為電著塗裝（electrodeposition coating)時則有 省略的情形。並且，如為磷酸鋅系化成處理時，以皮膜結 晶析出之微細化為目的，通常係在（2)與（3)之間使用磷酸 鈦或磷酸鋅之微粒子分散水溶液施行表面調整處理。 底塗處理係在處理液中添加界面活性劑之情形下可同 時進行脫脂與底塗皮膜的析出。例如在鍅系化成處理時， 曰本專利第4067103號公報中揭示一種脫脂兼化成處理 劑，其特徵係：由選自锆、鈦及铪所成組群中之至少一種、 4 322221 201107531 砉 • W及非離子性界面活性劑所構成，而該非離子性界面活 性劑之HLB值為9至17，固形分之含量為2〇至3〇〇〇〇〇卿。 如為Θ酉夂鋅系化成處理時，日本特開2剛_87254號公 報中揭不-種吸附油分之鋼材的脫脂兼具鱗酸鋅化成處理 液，其特徵係.含有鋅離子、磷酸根離子以及化成促進劑 且含有以HLB12至π之聚氧伸乙基烷基醚乳化之礦物油 .〇. 1 至 10g/L 者。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利第4067103號公報 [專利文獻2]日本特開2〇〇〇_87254號公報 【發明内容】 · [發明所欲解決之課題] 在使用先前技術中之锆系化成處理之同時的脫脂化成 處理時，由於所析出之皮膜為含水率高的非晶質，因此， 吸附在金屬材料表面之部分油分與界面活性劑一起被皮膜 所吸收’而此即使在化成處理後之水洗中亦無法完全去 =三故有塗膜密著性不足的情形。更且，塗裝如為陽離子 裝時，相較於磷酸鋅系化成處理者，則有附塗裝之 解者色分佈力低劣的缺點。 夕卜 理時，，在使用磷酸鋅系化成處理之同時的脫脂化成處 队 m由於所析出之皮膜為結晶質而使油分不被皮膜所吸 收· ’因而必項少 表= 4’略一般磷酸鋅系化成處理步驟中所適用的 s° '驟’故皮膜結晶粗大，而有變的無法獲得充分 322221 5 201107531 之塗膜密著性的缺點。 [用以解決課題之手段] 本發明者等以解決上述課題為目的而專心致志進行檢 讨，發現出該解決方法。亦即，本發明係如下（1)至（4)所 示者。 (1) 一種金屬表面處理液，係含有Bi離子1〇至1000ppm以 及3價Fe離子1〇〇至2〇〇〇ppm，且[2XBi離子濃度價Fe 離子濃度]為500至3000ppm，更且，含有充分可溶化Bi 與Fe之螯合劑以及界面活性劑之pH3至14的水溶液。 (2) 如上述（1)之金屬表面處理液，其中，含有1〇至卯⑴ 之1種或2種以上選自Mg離子、Ca離子、Zn離子以及M 離子者。 (3) —種表面處理方法，係對預先吸附油分之金屬材料，藉 由以上述（1)或（2)之處理劑處理金屬材料，即可將去除油 分之脫脂處理以及丨至別⑽^之以析出的底塗處理在相 同步驟中進行。 (4) 一種金屬材料，係經（3)之方法處理者。 [發明之效果] 如依本發明，除了可將表面淨化處理（脫脂）與底塗處 理在相同步驟中進行以外，並可於該處理後之塗震步驟中 達成優異的塗膜密著性與耐银性之效果。 【實施方式】 本發明中所適用之金屬材料係以冷乳鋼板、熱乾鋼 板、鑄材、鋼線'鋼管等鋼材；藉由溶融鑛敷法、電鍵法、 322221 201107531 …鍍法施行鋅艘數之鋼材；鋅麗矯以及㉞合金板等為佳。 另外辞鍍敷亦可為經Fe、A1、Ni、处等之合金成分合金 ^的辞°金鍍數。惟鮮電極電位高於Bi之如銅或銀的金 屬並不佳。 八本發3以金屬材料之表面吸附有防鏽油、沖壓油等 刀者為引提，可對如此材料而同時進行脫脂處理與底塗 處為心月之特徵，即使預先使表面淨化之金屬材料為適 用，亦不降低本發明之效果。 本發明之處理液係含有Bi離子10至1000 ppm。以20 至7〇〇 PPm更佳，50至500 ppm最佳。由電化學系列之觀 點而言’由於Bi之標準電極電位高於Fe、Zn、A1等金屬， 因此，金屬材料表面於處理液中溶出時，金屬狀Bi置換析 出。該金屬狀Bi作為底塗皮膜而發揮與磷酸鋅系化成皮膜 或結系化成皮膜為同等以上之性能。處理液中之Bi離子濃 度低於下限時’所析出Bi的吸附量不足，使蜜裝後之耐姓-性以及塗膜密著性變的不充分。高於上限時，Bi的吸附量 過剩’使得塗膜密著性降低。另外，處理液中之Bi離子濃 度可經高頻感應耦合電漿質譜分析（ICP)或原子吸光分光 分析（AA)等而定量分析。201107531 VI. Description of the Invention: [Technical Field] The present invention relates to a metal surface treatment liquid and a metal surface treatment method using the same, which is used for surface cleaning of a metal material in the same step Treatment liquid for treatment (degreasing) and pretreatment of Painting. [Prior Art] When the metal material is coated, it is usually subjected to a primer treatment before coating for the purpose of improving the adhesion of the coating film and the corrosion resistance after coating. In particular, when a sheet metal structure having a complicated shape is formed by stamping or welding, a base treatment process of a chemical conversion treatment type excellent in throwing power of electrolytic coloring, such as a zinc phosphate system, is widely used. Chemical treatment or sputum formation treatment. The general processing steps of the primer treatment are (1) degreasing - (2) water washing - (3) primer treatment - (4) water washing - (5) drying, and the water washing steps of (2) and (4) can be carried out as needed. In many stages, it can also be used for hot water washing. Further, the drying step of (5) is omitted if it is continuously applied as an electrodeposition coating. In the case of the zinc phosphate-based chemical conversion treatment, for the purpose of refining the film crystallization, a surface adjustment treatment is usually carried out using a fine particle-dispersed aqueous solution of titanium phosphate or zinc phosphate between (2) and (3). In the primer treatment, the degreasing and the deposition of the undercoat film can be simultaneously performed in the case where a surfactant is added to the treatment liquid. For example, in the case of the oxime-based chemical conversion treatment, a degreasing and chemical conversion treatment agent is disclosed in the patent system, which is characterized in that it is at least one selected from the group consisting of zirconium, titanium and hafnium, 4 322221 201107531 砉 • W and a nonionic surfactant are used, and the nonionic surfactant has an HLB value of 9 to 17, and a solid content of 2 to 3 Å. In the case of the bismuth zinc-based chemical conversion treatment, the degreasing and scalar zinc chemical conversion treatment liquid of the steel which adsorbs oil is disclosed in Japanese Laid-Open Patent Publication No. _87254, which is characterized in that it contains zinc ions and phosphates. Ion and a chemical accelerator and a mineral oil emulsified by a polyoxyalkylene ether ether of HLB 12 to π. 1. 1 to 10 g/L. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 4,067,103 [Patent Document 2] Japanese Patent Application Laid-Open No. Hei No. Hei. When the degreasing treatment is carried out using the zirconium chemical conversion treatment in the prior art, since the deposited film is amorphous having a high water content, part of the oil adsorbed on the surface of the metal material is coated with the surfactant together with the surfactant. Absorption', and even in the water washing after the chemical treatment, it is impossible to completely go to the case where the coating film is insufficiently sealed. Further, when the coating is cationic, the color distribution of the coated coating is inferior to that of the zinc phosphate-based chemical conversion processor. In the case of the use of the zinc phosphate-based chemical conversion treatment, the degreasing and forming unit m is such that the deposited film is crystalline and the oil is not absorbed by the film. Therefore, it is necessary to have a small amount of zinc. It is a s° 'sudden' applied to the processing step, so that the film crystal is coarse, and there is a disadvantage that the coating film adhesion of 322221 5 201107531 cannot be obtained. [Means for Solving the Problem] The inventors of the present invention have focused their efforts on the purpose of solving the above problems, and found the solution. That is, the present invention is as shown in the following (1) to (4). (1) A metal surface treatment liquid containing 1 to 1000 ppm of Bi ions and 1 to 2 ppm of trivalent Fe ions, and [2XBi ion concentration and Fe ion concentration] is 500 to 3000 ppm, and further, An aqueous solution containing a chelating agent of sufficiently soluble Bi and Fe and a pH of 3 to 14 of a surfactant. (2) The metal surface treatment liquid according to the above (1), which contains one or more selected from the group consisting of Mg(R), Ca ion, Zn ion and M ion. (3) A surface treatment method for a metal material which adsorbs oil in advance, by treating the metal material with the treatment agent of the above (1) or (2), the degreasing treatment for removing the oil and the mashing to the other (10) The primer treatment with precipitation is carried out in the same step. (4) A metal material which is treated by the method of (3). [Effects of the Invention] According to the present invention, in addition to the surface purification treatment (degreasing) and the primer treatment in the same step, excellent coating film adhesion can be achieved in the coating step after the treatment. The effect of silver resistance. [Embodiment] The metal material to which the present invention is applied is a steel material such as a cold-milk steel plate, a hot-dry steel plate, a cast material, a steel wire 'steel pipe, or the like; and a zinc ship is used by a molten ore method, a key method, and a 322221 201107531 ... plating method. The number of steel; zinc rectification and 34 alloy plates are preferred. Further, the plating may be a gold plating number of the alloy composition of Fe, A1, Ni, and the like. However, metals with a higher electrode potential than Bi such as copper or silver are not good. Eight Benfa 3 is based on the adsorption of anti-rust oil and stamping oil on the surface of the metal material. The degreasing and undercoating of the material can be simultaneously characterized by the heart, even if the surface is cleaned beforehand. The materials are suitable and do not detract from the effects of the present invention. The treatment liquid of the present invention contains Bi ions in an amount of 10 to 1000 ppm. It is better to use 20 to 7 〇〇 PPm and 50 to 500 ppm. From the viewpoint of the electrochemical series, since the standard electrode potential of Bi is higher than that of metals such as Fe, Zn, and A1, when the surface of the metal material is eluted in the treatment liquid, the metal Bi is displaced and precipitated. This metal-like Bi exhibits performance equivalent to or higher than that of the zinc phosphate-based film or the knot-forming film as the undercoat film. When the concentration of Bi ions in the treatment liquid is lower than the lower limit, the amount of adsorption of Bi precipitated is insufficient, and the resistance to the surname and the adhesion of the coating film after the honey-filling are insufficient. When the ratio is higher than the upper limit, the amount of adsorption of Bi is excessive, so that the coating film adhesion is lowered. Further, the concentration of Bi ions in the treatment liquid can be quantitatively analyzed by high frequency inductively coupled plasma mass spectrometry (ICP) or atomic absorption spectrometry (AA).
Bi離子之供給可適用（1)使硝酸Bi等可溶性Bi鹽溶 解於水之方法、（2)使氧化Bi或金屬Bi溶解於硝酸、硫酸、 鹽酸等無機酸之方法、（3)使氧化Bi或金屬Bi溶解於適用 作為螯合劑之有機酸的方法中之任一種，惟以無需剩餘的 無機酸分之點而言’以（3)之方法為佳。 7 322221 201107531 本發明之處理液係含有3價Fe離子100至2000ppm。 以 200 至 1700 ppm 更佳，300 至 1500 ppm 最佳。3 價 Fe 離子本身具有藉由還原成2價而促進金屬從金屬材料表面 溶出之作用。亦即，係作為促進金屬材料氧化之氧化劑而 作用者。作為氧化劑之作用係，不僅調控Bi之析出，並具 有將先前附著於金屬材料表面之油分的油分去除性加以提 高之作用，因此對於吸附有油分之金屬材料，3價Fe離子 即成為必要成分。3價Fe離子濃度低於下限時，隨著Bi 之吸附量不足而使油分去除性降低。高於上限時，則過度 蝕刻，Bi之析出效率降低。另外，溶液中之3價Fe離子 濃度可由全部的Fe離子濃度減去2價Fe離子濃度而求 得。全部的Fe離子濃度係與Bi離子濃度相同，可經高頻 感應耦合電漿質譜分析（ICP)或原子吸光分光分析（AA)等 而定量分析。並且，2價Fe離子濃度可經鄰啡啉吸光光度 法等而定量。惟，2價Fe離子在本處理液之pH範圍中經 溶存氧的作用而較快速地氧化成3價Fe離子-，因此，實質 上3價Fe離子成為與全部的Fe離子濃度為相同之值。 3價Fe離子之供給一般係使硫酸鐵、硝酸鐵、氯化鐵 等3價Fe之鹽溶解的方法，在處理表面存在有Fe之金屬 材料時，經由處理而自動地補給。金屬F e經處理而溶出於 處理液中時，首先雖成為2價Fe離子，惟如前所述，在本 處理液之pH範圍中，經溶存氧的作用而較快速地氧化成3 價F e離子。 本發明之處理液中，[2xBi離子濃度+3價Fe離子濃度] 8 322221 201107531 為 500 至 3000ppm。以 700 至 2500ppm 為佳，1 000 至 2000ppm 更佳。低於下限時，隨著Bi之吸附量不足而使油分去除性 降低。高於上限時，則過度蝕刻，Bi之析出效率降低。另 外，[2xBi離子濃度+3價Fe離子濃度]之單位雖為ppm， 然已不具濃度之意而可視為指數。本發明者等發現出Bi離 子濃度與3價Fe離子濃度之和對於金屬材料的蝕刻力與 Bi吸附量之控制為重要因素，惟由於Bi離子濃度之決定 係數高於3價Fe離子濃度，因此，在Bi離子濃度乘以係 數2並加上3價Fe離子濃度之情形下，成為更釐定本發明 之處理液的適當範圍之適合指數。 本處理液含有螯合劑。Bi —般在ρΗ2以下時雖作為離 子而溶解，然在其上之pH範圍中並不溶解。即便使暫時在 pH2以下之水溶液中溶解，但藉由臉中和而使pH上升時， 則經水解而沉殿為氫氧化物。因此，在作成pH3以上之水 溶液時，經螯合劑的添加而使Bi螯合不得不安定化。螯合 劑可適用各種有機酸或有機酸之鹼金屬鹽。具體而言，係 以乙酸、馬來酸、富馬酸等羧酸；檸檬酸、蘋果酸、羥乙 酸等羥基羧酸；甘胺酸、半胱胺酸、麩胺酸等胺基酸；EDTA、 NTA、HEDTA等胺基多元羧酸；HEDP、EDTMP等有機磺酸； 試鈦靈（Tiron)等羥基磺酸；以及該等之鹼金屬鹽為適用。 並且，除有機酸外，亦可使用鄰苯二酚、對苯二酚之酚類 作為螯合劑。另外，.該等之中，在使用胺基酸，特別是半 胱胺酸時，在對所析出之Bi的基層金屬的密著性優異之點 上為佳。 9 322221 201107531 該等螯合劑直接溶解於水中。螯合劑水溶液為酸性 時，使Bi或Fe的氫氧化物' 氧化物、金屬溶解於螯合劑 水溶液中，可作成本發明之處理液。 螯合劑之滚度並無特別規定，惟以1〇〇〇至5_卿左 :為佳。依處理液中之金屬離子濃度、螯合劑種類(分子 量:配位基數、與各種金屬離子的安定度常數）、處理液 H而決定θ所需要的最小添加量，過量的添加並無技術上 的弊害，而是由經濟因素所決定。 本發明之處理液含有界面活性劑。由於本發明係以在 金屬材料表面吸附有防鏽油、賴油等油分為前提，因此， 界面活性劑係用以將其予以乳化分散而添加。界面活性劑 ^致分為陰離子系、陽離子系、非離子系3種，其中，以 環氧燒（alkylene oxide)作為親水基之非離子系界面活性 劑在洗淨性優異之點上為佳。非離子系界面活性劑之中亦 以依tiffin法之HLB值在u至15之範圍更佳。然而， 為了消泡效果及洗淨性之相乘效果亦可併用則未達^之 非離子系界面活㈣。界面活性狀漠度並無特別規定， 惟以100至5000_為佳，以2〇〇至侧卿更佳又以 500至3000ppm為最佳。如低於下限則洗淨性不足，而高 於上限時’洗淨性之提高效果為飽和之同時，反而減少以 之析出量，因而不佳。 本發明之處理液為pH3至14之水溶液。處理液之pH 以4至13更佳’以5至12為最佳。處理液之pH低於下限 時，金屬材料將會降度地蝕刻而降低Bi的析出效率。如高 322221 201107531 於上限時，因螯合劑的影響而使Bi的安定化作用降低，會 有Bi之氫氧化物沉澱的情形。並且，特別是金屬材料為鋼 材時，對於基底金屬之蝕刻力漸行降低，而減少Bi的析出 量。處理液之pH可經任意的鹼或酸而調整。適用之鹼可為 氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、氨水、碳酸氫 銨等，適用之酸可為硫酸、硝酸、鹽酸等無機酸；乙酸、 檸檬酸、EDTA等有機酸。另外，上述螯合劑亦可作為pH 調整用之有機酸使用。 本發明之處理液中在另含有Mg離子、A1離子、Ca離 子、Zn離子的情形下，可使塗裝後之耐蝕性以及塗膜密著 性更加提高。該等金屬離子濃度並無特別規定，以10至 5000ppm 為佳，以 30 至 3000ppm 更佳，尤以 200 至 2000ppm 為最佳。雖然對於該等金屬離子之作用效果的内容並不清 楚，咸認為應是所析出Bi之細緻化而提高對金屬材料表面 之密著力的效果所致。 本發明之處理液除了處理金屬材料之處理液本身以 外，亦包含在處理時將失去之成分補給至處理液的組成 物。金屬材料經由本發明之處理液處理時，由於吸附在金 屬材料表面之處理液本身被攜至下個步驟，且吸附在金屬 材料表面之Bi亦被攜出，因此，相較於處理液中之其他成 分，以較多的比例補給B i。如此，用以維挤處理液組成所 補給之液的組成，不一定侷限於與處理液相同之組成。更 且，在補給濃度高於處理液之組成物時，假定以2種以上 之包裝補給時等，該等亦均解釋為本發明之處理液。 11 322221 201107531 對於本發明之處理液的溫度雖無特別規定，惟以25至 60°C為佳。以30至55°C更佳，以35至50°C為最佳。處理 液溫度低於下限時，不僅Bi之析出量減低且損及脫脂性。 處理液溫度高於上限時，會有Bi吸附量過多的情形。 對於本發明之處理時間雖無特別規定，惟以30至300 秒為佳。以60至200°C秒更佳，以90至180°C秒為最佳。 處理時間低於下限時，不僅Bi之析出量減低且損及脫脂 性。處理時間高於上限時，會有Bi吸附量過多的情形。 在使本發明之處理液適用於金屬材料時，至少須使處 理液與金屬材料表面接觸，惟該方法亦以浸潰法、喷霧法 之任一種方法均適用。並且，亦可組合浸潰處理與喷霧處 理以進行處理。浸潰處理時，亦可部分地或整體地將金屬 材料作為陰極而進行電解。更且，為提高油分去除性亦可 適用超音波。 在使用本發明之處理液處理金屬材料時所析出之Bi 吸附量係以1至200mg/m2為佳。以5至100mg/m2更佳，以 10至50mg/m2為最佳。吸附量低於下限時，塗裝後之耐蝕 性會降低，高於上限時，會損及塗裝後之塗膜密著性。The supply of Bi ions can be applied to (1) a method of dissolving a soluble Bi salt such as Bi nitrate in water, (2) a method of dissolving Bi or Bi in a chemical solution such as nitric acid, sulfuric acid or hydrochloric acid, and (3) oxidizing Bi. Or the metal Bi is dissolved in any one of the methods suitable for the organic acid as a chelating agent, but the method of (3) is preferred in that the remaining inorganic acid is not required. 7 322221 201107531 The treatment liquid of the present invention contains trivalent Fe ions in an amount of 100 to 2000 ppm. More preferably from 200 to 1700 ppm, and from 300 to 1500 ppm. The trivalent Fe ion itself has a function of promoting metal elution from the surface of the metal material by reduction to divalent. That is, it acts as an oxidizing agent that promotes oxidation of a metal material. The action of the oxidizing agent not only regulates the precipitation of Bi, but also has an effect of improving the oil removal property of the oil component previously attached to the surface of the metal material. Therefore, trivalent Fe ions become an essential component for the metal material to which the oil component is adsorbed. When the trivalent Fe ion concentration is lower than the lower limit, the oil removal property is lowered as the amount of adsorption of Bi is insufficient. When it is higher than the upper limit, it is excessively etched, and the precipitation efficiency of Bi is lowered. Further, the trivalent Fe ion concentration in the solution can be obtained by subtracting the divalent Fe ion concentration from the total Fe ion concentration. The total Fe ion concentration is the same as the Bi ion concentration, and can be quantitatively analyzed by high frequency inductively coupled plasma mass spectrometry (ICP) or atomic absorption spectrometry (AA). Further, the divalent Fe ion concentration can be quantified by o-phenanthroline spectrophotometry or the like. However, the divalent Fe ions are rapidly oxidized to the trivalent Fe ions by the action of dissolved oxygen in the pH range of the treatment liquid, and therefore, the substantially trivalent Fe ions have the same value as the total Fe ion concentration. . The supply of trivalent Fe ions is generally a method of dissolving a salt of trivalent Fe such as iron sulfate, iron nitrate or ferric chloride, and is automatically replenished by treatment when a metal material of Fe is present on the treated surface. When the metal F e is treated and dissolved in the treatment liquid, it first becomes a divalent Fe ion, but as described above, in the pH range of the treatment liquid, it is rapidly oxidized to a trivalent F by the action of dissolved oxygen. e ion. In the treatment liquid of the present invention, [2xBi ion concentration + trivalent Fe ion concentration] 8 322221 201107531 is 500 to 3000 ppm. It is preferably 700 to 2500 ppm, more preferably 1 000 to 2000 ppm. When the amount is lower than the lower limit, the oil removal property is lowered as the amount of adsorption of Bi is insufficient. When it is higher than the upper limit, it is excessively etched, and the precipitation efficiency of Bi is lowered. Further, although the unit of [2xBi ion concentration + trivalent Fe ion concentration] is ppm, it can be regarded as an index without concentration. The inventors have found that the sum of the concentration of Bi ions and the concentration of trivalent Fe ions is an important factor for controlling the etching force of the metal material and the amount of Bi adsorption, but since the coefficient of determination of the concentration of Bi ions is higher than the concentration of the trivalent Fe ions, In the case where the Bi ion concentration is multiplied by the coefficient 2 and the trivalent Fe ion concentration is added, a suitable index for determining the appropriate range of the treatment liquid of the present invention is obtained. This treatment liquid contains a chelating agent. Bi is generally dissolved as an ion when it is below ρ Η 2, but does not dissolve in the pH range above it. Even if it is temporarily dissolved in an aqueous solution having a pH of 2 or less, when the pH is raised by the neutralization of the face, the hydroxide is hydrolyzed to form a hydroxide. Therefore, when an aqueous solution having a pH of 3 or higher is prepared, the addition of a chelating agent causes the Bi sequestration to be stabilized. The chelating agent can be applied to various organic or organic acid alkali metal salts. Specifically, it is a carboxylic acid such as acetic acid, maleic acid or fumaric acid; a hydroxycarboxylic acid such as citric acid, malic acid or glycolic acid; an amino acid such as glycine, cysteine or glutamic acid; EDTA; , an amine-based polycarboxylic acid such as NTA or HEDTA; an organic sulfonic acid such as HEDP or EDTMP; a hydroxysulfonic acid such as Tiron; and the alkali metal salt are suitable. Further, in addition to the organic acid, phenols of catechol and hydroquinone may be used as a chelating agent. Further, among these, when an amino acid, particularly cysteine, is used, it is preferable in that the adhesion to the base metal of the precipitated Bi is excellent. 9 322221 201107531 These chelating agents are dissolved directly in water. When the aqueous solution of the chelating agent is acidic, the hydroxide or metal of Bi or Fe is dissolved in the aqueous solution of the chelating agent, and it can be used as the treatment liquid of the invention. There is no special regulation on the rolling rate of the chelating agent, but it is preferably 1〇〇〇 to 5_卿 left: Depending on the metal ion concentration in the treatment liquid, the type of chelating agent (molecular weight: number of coordination groups, stability constant with various metal ions), and treatment liquid H, the minimum addition amount required for θ is determined, and excessive addition is not technically required. The harm is determined by economic factors. The treatment liquid of the present invention contains a surfactant. Since the present invention is based on the premise that oil such as rust preventive oil or lyophilic oil is adsorbed on the surface of the metal material, the surfactant is used to emulsify and disperse it. The surfactant is classified into three types, anionic, cationic, and nonionic. Among them, a nonionic surfactant having an alkylene oxide as a hydrophilic group is preferred because it has excellent detergency. Among the nonionic surfactants, the HLB value by the tiffin method is preferably in the range of u to 15. However, in order to achieve the synergistic effect of the defoaming effect and the detergency, it is also possible to use a non-ionic interface (4). There is no special regulation on the activity of the interface, but 100 to 5000 Å is preferred, and 2 〇〇 to the side is better and 500 to 3000 ppm is the best. If the temperature is lower than the lower limit, the detergency is insufficient, and when the upper limit is higher than the upper limit, the effect of improving the detergency is saturated, and the amount of precipitation is decreased, which is not preferable. The treatment liquid of the present invention is an aqueous solution of pH 3 to 14. The pH of the treatment liquid is preferably from 4 to 13 and is preferably from 5 to 12. When the pH of the treatment liquid is lower than the lower limit, the metal material will be etched with a reduced degree to lower the precipitation efficiency of Bi. If the height is 322221 201107531, the stability of Bi is lowered due to the influence of the chelating agent, and there is a case where the hydroxide of Bi is precipitated. Further, particularly when the metal material is a steel material, the etching power to the base metal is gradually lowered to reduce the amount of precipitation of Bi. The pH of the treatment liquid can be adjusted by any base or acid. Suitable bases may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, ammonia water, ammonium hydrogencarbonate, etc. Suitable acids may be inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, etc.; organic acids such as acetic acid, citric acid, EDTA, etc. . Further, the above chelating agent can also be used as an organic acid for pH adjustment. When the treatment liquid of the present invention further contains Mg ions, A1 ions, Ca ions, and Zn ions, the corrosion resistance after coating and the coating film adhesion can be further improved. The concentration of the metal ions is not particularly limited, and is preferably from 10 to 5,000 ppm, more preferably from 30 to 3,000 ppm, particularly preferably from 200 to 2,000 ppm. Although the content of the effect of the metal ions is not clear, it is considered that the effect of the precipitation of Bi is increased to improve the adhesion to the surface of the metal material. The treatment liquid of the present invention contains, in addition to the treatment liquid itself for treating the metal material, a composition which replenishes the lost component to the treatment liquid during the treatment. When the metal material is treated by the treatment liquid of the present invention, since the treatment liquid adsorbed on the surface of the metal material itself is carried to the next step, and Bi adsorbed on the surface of the metal material is also carried out, it is compared with the treatment liquid. Other ingredients are supplied to B i in a larger proportion. Thus, the composition of the liquid to be replenished by the composition of the treatment liquid is not necessarily limited to the same composition as the treatment liquid. Further, when the supply concentration is higher than the composition of the treatment liquid, it is assumed that the treatment liquid is supplied in two or more types of packages, and the like. 11 322221 201107531 The temperature of the treatment liquid of the present invention is not particularly limited, but is preferably 25 to 60 °C. More preferably from 30 to 55 ° C, and most preferably from 35 to 50 ° C. When the temperature of the treatment liquid is lower than the lower limit, not only the precipitation amount of Bi is lowered but also the degreasing property is impaired. When the temperature of the treatment liquid is higher than the upper limit, there is a case where the amount of Bi adsorption is excessive. Although the processing time of the present invention is not particularly specified, it is preferably 30 to 300 seconds. It is preferably 60 to 200 ° C sec and 90 to 180 ° C sec. When the treatment time is lower than the lower limit, not only the precipitation amount of Bi is lowered but also the degreasing property is impaired. When the treatment time is higher than the upper limit, there is a case where the amount of Bi adsorption is excessive. When the treatment liquid of the present invention is applied to a metal material, at least the treatment liquid must be brought into contact with the surface of the metal material, but the method is also applicable to any one of a dipping method and a spray method. Further, the impregnation treatment and the spray treatment may be combined to perform the treatment. In the case of the impregnation treatment, the metal material may be partially or entirely electrolyzed as a cathode. Furthermore, ultrasonic waves can be applied to improve oil removal. The amount of Bi adsorbed in the treatment of the metal material using the treatment liquid of the present invention is preferably from 1 to 200 mg/m2. More preferably, it is 5 to 100 mg/m2, and most preferably 10 to 50 mg/m2. When the adsorption amount is lower than the lower limit, the corrosion resistance after coating is lowered, and when it is higher than the upper limit, the coating film adhesion after coating is impaired.
Bi係作為如上述之金屬而由金屬材料表面析出，惟與 其它金屬同樣地析出之金屬Bi的最表面則較快速地氧 化。因此，特別是經水洗後之乾燥步驟及塗裝後的焙烤步 驟等而有熱履歷時，以分析上不可忽視之比例而可確認氧 化物的存在。 本發明之金屬材料一般經快速地水洗、瀝水乾燥後施 12 322221 201107531 盯塗裝。然而，塗裝如為電著塗裝時，則可省略瀝水乾燥。 由於本發明之金屬材料已吸附著具有作為底塗皮膜之效果 的Bl ’因此無須特別地施行如磷酸鋅系化成處理或鍅系化 成地之底塗處理，惟不會因Bi而降低該等化成處理之處 理丨生反之’亦不會因該等之化成處理而減少Bi的效果。 [實施例] 以下列舉實施例及比較例以具體地說明本發明。 試驗板之製作： 試驗板係使用冷軋鋼板：SPCC SD(JIS G 3141)以及合 金化'溶融鋅鍍敷鋼板：SGCD3 SMO F06(JIS G 3302)，為了 固定吸附油之條件，在溶劑脫脂後以輥塗機盡上防鏽油： NOX-RUST550HN(Parker Industries，Inc.製造）1.5g/m2, 於室内放置10天。 處理液之製作： 使螯合劑僅成為10重量％之量而於去離孑水中溶解， 加溫至50°C之狀態，一面搜拌一面添加規定量之氧化Bi， 使溶解至固形物全無。將3價Fe離子作為梢酸鐵9水合 物’並將其它之添加金屬分別作為確酸會，分別定量添加 作為非離子系界面活性劑之聚氧伸烷基炫基醚（HLB : 14. 1)’最後以氫氧化鈉調整pH。處理液之組成呈示於表1。 13 322221 201107531 [表1]實施例及比較例 處理液 Bi附著量 塗裝性能 賞施例及 佥屬 Bi離子 [ppm] 3價Fe tt子 [ppm] 2xBi+Fe [ppm] ft合劑 添加金屬 界面活性 比枚例 材料 種類 濃度[ppm] [ppm] 剤滚度 [ppm] pH [mg/m2] 密著性 耐蝕性 實施例1 SP 100 1000 1200 HEDTA 2000 Ca : 15 _ 5.2 20 ◎ ◎ 實施例2 SP 500 1900 2900 EDTA 5000 - 550 5.5 167 〇 ◎ 賞铯例3 SP 12 480 504 檸橄酸 2000 - 2800 6.0 3 ◎ 〇 實砲例4 SP 900 110 1910 HEDTA 5000 - 2000 6.5 185 〇 ◎ 賞拖例5 SP 40 1600 1680 試鈦靈 4000 Zn : 1500 3500 6.5 12 ◎ ◎ 賞施例6 CA 40 1600 1680 HEDTA 3000 Zn ： 1500 3500 6.5 25 ◎ ◎ 實狍例7 SP G00 250 1450 HEDTA 5000 A1 ： 50 2000 4.5 88 ◎ ◎ 實施例8 SP 70 800 940 EDTMP 3000 - 400 11.5 14 ◎ ◎ 實拖例9 GA 70 800 940 EDTHP 3000 - 400 11.5 22 ◎ ◎ 1Γ施洌】0 SP 90 900 1080 半胱胺酸 4500 Zn ： 1000 500 9.0 20 ◎ ◎ 實施例11 SP 200 1700 2100 半胱胺酸 4000 Zn: 1000 2000 7.0 45 ◎ ◎ 實施例12 SP 200 1300 1700 乙酸 3500 Mg : 500 2000 6.0 42 ◎ ◎ T铯例13 SP 150 1000 1300 EDTMP 3000 - GOO 10.0 35 ◎ ◎ 比較例1 SP 8 2100 2116 HEDTA 4000 - 2000 6.5 0.8 〇 X 比較例2 SP 1100 90 2290 HEDTA 5000 - 2000 6.5 205 X Δ 比較例3 SP 50 300 400 EDTMP 2000 - 1000 12.5 0.8 〇 X 比枚例4 GA 800 1800 3400 HEDTA 1500 - 1500 2.5 251 X 〇 比較例5 SP - - - 一 - :500, Zn:500 2000 3.5 - X Δ SP :冷軋鋼板 GA:合金化溶融鋅鍍敷銅板 另外，對於比較例5，在分別添加500ppm之結氫氟酸 作為Zr、500ppm之硝酸鋅作為Zn、lOppm之亞琐酸納、 2000ppm之聚氧伸乙基烷基醚（HLB : 12. 5)以及僅使最後之 硝酸離子濃度成為3500ppm的硝酸鈉後，使用經氫氧化鈉 調整pH成為3. 5之處理液，在45°C浸潰處理120秒鐘。 該處理相當於專利文獻1之實施例1。 經本發明之處理劑的處理： 將本發明之處理劑加溫至40°C，並將試驗板浸潰處理 14 322221 201107531 、 120秒鐘。處理後之試驗板立即於去離子水中水洗，使用 電烘箱於80°C乾燥所吸附之水分。Bi is precipitated as a metal as described above from the surface of the metal material, but the outermost surface of the metal Bi precipitated in the same manner as the other metal is rapidly oxidized. Therefore, in particular, when there is a heat history in the drying step after washing with water and the baking step after coating, the presence of the oxide can be confirmed by a ratio which cannot be ignored in analysis. The metal material of the present invention is generally subjected to rapid water washing, draining and drying, and then applied to 12 322221 201107531. However, if the coating is applied by electro-coating, the draining may be omitted. Since the metal material of the present invention has adsorbed B1 having an effect as a primer film, it is not necessary to specifically perform a primer treatment such as a zinc phosphate-based chemical conversion treatment or a lanthanide-based formation, but does not reduce the formation due to Bi. The treatment process is reversed and the effect of Bi is not reduced by the processing of such a process. [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples. Production of test panels: The test panels were cold-rolled steel sheets: SPCC SD (JIS G 3141) and alloyed 'zinc-zinc plated steel sheets: SGCD3 SMO F06 (JIS G 3302), in order to fix the conditions of adsorbed oil, after solvent degreasing The rust preventive oil was applied by a roll coater: NOX-RUST550HN (manufactured by Parker Industries, Inc.) at 1.5 g/m2, and allowed to stand indoors for 10 days. Preparation of treatment liquid: The chelating agent is dissolved in deionized water only in an amount of 10% by weight, and heated to 50 ° C, and a predetermined amount of oxidized Bi is added while mixing to dissolve the solid matter. . The trivalent Fe ion is used as the iron sulphate 9 hydrate and the other added metals are respectively used as the acid, and the polyoxyalkylene ether ether as a nonionic surfactant is separately added (HLB: 14. 1 ) ' Finally adjust the pH with sodium hydroxide. The composition of the treatment liquid is shown in Table 1. 13 322221 201107531 [Table 1] Examples and Comparative Examples Treatment liquid Bi adhesion amount Coating performance Appreciation example and bismuth Bi ion [ppm] Trivalent Fe tt sub-[ppm] 2xBi+Fe [ppm] ft mixture addition metal interface Activity ratio sample material concentration [ppm] [ppm] 剤 rolling degree [ppm] pH [mg/m2] Adhesion corrosion resistance Example 1 SP 100 1000 1200 HEDTA 2000 Ca : 15 _ 5.2 20 ◎ ◎ Example 2 SP 500 1900 2900 EDTA 5000 - 550 5.5 167 〇 ◎ Reward Example 3 SP 12 480 504 Limemic Acid 2000 - 2800 6.0 3 ◎ 〇 炮 4 4 SP 900 110 1910 HEDTA 5000 - 2000 6.5 185 〇 ◎ 赏 拖 5 SP 40 1600 1680 Test Titanium 4000 Zn : 1500 3500 6.5 12 ◎ ◎ Appreciation Example 6 CA 40 1600 1680 HEDTA 3000 Zn : 1500 3500 6.5 25 ◎ ◎ Example 7 SP G00 250 1450 HEDTA 5000 A1 : 50 2000 4.5 88 ◎ ◎ Example 8 SP 70 800 940 EDTMP 3000 - 400 11.5 14 ◎ ◎ Real drag example 9 GA 70 800 940 EDTHP 3000 - 400 11.5 22 ◎ ◎ 1 Γ 洌 】 0 SP 90 900 1080 Cystein acid 4500 Zn : 1000 500 9.0 20 ◎ ◎ Example 11 SP 200 1700 2100 Cystelic acid 4000 Zn: 1000 20 00 7.0 45 ◎ ◎ Example 12 SP 200 1300 1700 Acetic acid 3500 Mg : 500 2000 6.0 42 ◎ ◎ T 铯 Example 13 SP 150 1000 1300 EDTMP 3000 - GOO 10.0 35 ◎ ◎ Comparative Example 1 SP 8 2100 2116 HEDTA 4000 - 2000 6.5 0.8 〇X Comparative Example 2 SP 1100 90 2290 HEDTA 5000 - 2000 6.5 205 X Δ Comparative Example 3 SP 50 300 400 EDTMP 2000 - 1000 12.5 0.8 〇X Specific Example 4 GA 800 1800 3400 HEDTA 1500 - 1500 2.5 251 X 〇 Comparison Example 5 SP - - - - - 500, Zn: 500 2000 3.5 - X Δ SP : Cold-rolled steel sheet GA: alloyed zinc-plated copper plate. In addition, for Comparative Example 5, 500 ppm of hydrofluoric acid was added as Zr, 500 ppm of zinc nitrate as Zn, 10 ppm of sodium succinate, 2000 ppm of polyoxyethylene ethyl ether (HLB: 12. 5), and only the final nitrate ion concentration of 3500 ppm of sodium nitrate The sodium hydroxide was adjusted to have a pH of 3.5, and the solution was immersed at 45 ° C for 120 seconds. This processing corresponds to the first embodiment of Patent Document 1. Treatment by the treatment agent of the present invention: The treatment agent of the present invention was heated to 40 ° C, and the test plate was immersed for treatment at 14 322221 201107531 for 120 seconds. The treated test plate was immediately washed with water in deionized water, and the adsorbed moisture was dried at 80 ° C using an electric oven.
Bi吸附量之測定： 處理後之試驗板進行螢光X射線分光分析（XRF)測定 B i吸附量。 塗裝： 使用關西塗料社製造之陽離子電著塗料「GT-10LF」將 處理後之試驗板進行電著塗裝。電著塗料之k度為28°C、 電壓之施加條件係在30秒鐘内直線升壓至200V，然後在 200V維持150秒鐘。塗裝後之試驗板在水洗後.，使用電烘 箱在170°C中烘烤塗膜30分鐘。 塗裝性能評估： 在塗裝後之試驗板上以刀具橫切，以JIS Z 2371為基 準，進行鹽水喷霧試驗100小時。從鹽水喷霧試驗後所切 割之切面，測定最大生鏽幅寬，並依據下述評價基準進行 評價。 對冷軋鋼板之判定基準： 生鏽幅寬未達1.0mm :◎ 生鑛幅寬在1. 0mm以上且未達1. 5mm :〇 生鏽幅寬在1. 5mm以上且未達2. 0mm : △ 生鏽幅寬在2. Omm以上：X 對合金化熔融鋅鍍敷鋼板之判定基準： 生鏽幅寬未達0. 5mm : ◎ 生鏽幅寬在0. 5mm以上且未達1. 0mm :〇 15 322221 201107531 生鑛幅寬在l.Gmm以上且未達l 5_ ·· △ 生鐵幅寬在1. 5mm以上：X 塗膜密著性評價·· 使塗裴後之試驗板在去離子水之沸騰水中浸潰1小 夺然後在塗面上以刀具在1 1條間隔1 mm之平行線上劃垂 直線，成為100個棋盤狀之切面。接著，在棋盤狀之切面 部分貼上cellotape(註冊商標），將膠帶剝離後，將塗膜 之棋盤狀的切面之剝離個數依照下述評價基準進行評價。 0個：◎ 1至5個··〇 6至10個：△ 11個以上：X 【圖式簡單說明】 益。 【主要元件符號說明】 無。 322221Measurement of Bi adsorption amount: The treated test plate was subjected to fluorescent X-ray spectroscopic analysis (XRF) to determine the amount of adsorption of B i . Coating: The treated test panels were subjected to electrocoating using a cationic electrocoat "GT-10LF" manufactured by Kansai Paint Co., Ltd. The k-degree of the electrocoat was 28 ° C, and the voltage application conditions were linearly boosted to 200 V in 30 seconds and then maintained at 200 V for 150 seconds. After the coating, the test plate was washed with water, and the film was baked at 170 ° C for 30 minutes using an electric oven. Coating performance evaluation: A salt spray test was carried out for 100 hours on a test plate after coating with a cross-cutting tool and based on JIS Z 2371. From the cut surface after the salt spray test, the maximum rust width was measured and evaluated according to the following evaluation criteria. 0mm。 The rusted width is less than 1. 0mm and less than 2. 0mm The rust width is 0. 5mm or more and less than 1. 5. 毫米。 The rust width is less than 0. 5mm and not up to 1. 0mm : 〇15 322221 201107531 The width of the ore is above l.Gmm and does not reach l 5_ ·· △ The width of the pig iron is 1. 5mm or more: X Coating film adhesion evaluation · · After the test plate is applied The ionized water is immersed in boiling water and then immersed in a small line on the coated surface with a cutter on a parallel line of 1 1 intervals of 1 mm to form 100 checkerboard slices. Next, cellotape (registered trademark) was attached to the checkerboard-shaped cut surface portion, and after peeling off the tape, the number of peeling of the checkerboard-shaped cut surface of the coating film was evaluated in accordance with the following evaluation criteria. 0: ◎ 1 to 5 ··〇 6 to 10: △ 11 or more: X [Simple description of the diagram] Benefit. [Main component symbol description] None. 322221