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TW200303934A - Composition and process for the treatment of metal surfaces - Google Patents

Composition and process for the treatment of metal surfaces Download PDF

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Publication number
TW200303934A
TW200303934A TW092102988A TW92102988A TW200303934A TW 200303934 A TW200303934 A TW 200303934A TW 092102988 A TW092102988 A TW 092102988A TW 92102988 A TW92102988 A TW 92102988A TW 200303934 A TW200303934 A TW 200303934A
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Taiwan
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patent application
item
treatment solution
scope
tungstate
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TW092102988A
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Chinese (zh)
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TWI255863B (en
Inventor
Gerald Wojcik
Justin Girard
Robert Berry
Richard Bauer
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Macdermid Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

A method of forming a conversion layer on a metallic surface and a composition usable in the method are provided. The composition is an aqueous solution comprising a source of tungstate ions and a soluble material comprising zirconium. The method provides a conversion coating on a surface that can then be painted or otherwise treated. The conversion coatings of the present invention are minimally affected by heating and/or baking, unlike chromate conversion coatings of the prior art.

Description

200303934 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） - (一） 發明所屬之技術領域： 本發明係關於用以產生轉化塗層在金屬表面上之組成物 和方法。本發明的轉化塗料通常不含鉻且能改良經處理的 表面之抗腐蝕性以及乾燥的有機飾面至那些經處理的表面 上之黏附性。另外，本發明的轉化塗料極少受隨後之加熱 及/或烘烤步驟所影響。本發明可用於處理鋼和其他金屬， 但特別適合於處理鋅、鋅合金、鋁和鋁合金。 φ (二） 先前技術： 爲了形成塗層來保護金屬對抗腐蝕以及改良隨後施加之 乾燥有機飾面的黏附性，先前技藝中已建議適合金屬表面 之各種轉化塗料。此等轉化塗料係由使用各種化學品的溶 液來處理金屬表面而產生者，此等化學品溶液與表面產生 反應而形成所需要之塗層。常用之轉化塗料組成物通常包 括磷酸鹽和鉻酸鹽。 使用磷酸鹽轉化塗料，特別是使用在鋼上，係已經使用 ® 很久了。最簡單之磷酸鹽溶液包括可與鐵、鋁及/或鋅產生 反應而形成磷酸鹽轉化塗層之鹼金屬磷酸鹽的水溶液。雖 然在許多應用中，磷酸鹽轉化塗料能增加經處理的表面之 抗腐蝕性及隨後所施加之乾燥有機飾面之黏附性，但是需 要更佳之結果。 鉻酸鹽轉化塗料通常較磷酸鹽塗料產生遠較佳的抗腐飩 性和黏附性。然而，鉻酸鹽轉化塗料在高溫下不能提供良 -6- 200303934 好抗腐蝕性和黏附性。鉻酸鹽溶液通常包括六價及/或三價 鉻的水溶液以及其它添加劑。歷史上’八價鉻產生最佳性 能之鉻酸鹽轉化塗料。然而’二價鉻酸鹽技術之最近改進 容許三價鉻酸鹽與六價鉻酸鹽在性能上競爭。典型的鉻酸 鹽組成物及其製造方法揭示於美國專利案N 0 5，4 0 7，7 4 9號 和4,3 4 9，3 9 2號中，將其教旨倂入本文中以供參考。無論 如何，鉻業已被判定爲一種具有相當毒性之金屬且予以嚴 格管制。其結果是，使用甚大的努力欲以不含鉻之塗料代 替鉻酸鹽塗料。 (三）發明內容： 因此，本發明之目的在提供一種能產生轉化塗層在金屬 表面上之組成物和方法，該塗層可提供優良抗腐蝕性和對 乾燥有機飾面之黏附性，而且無鉻含量。另外，本發明的 一目的在提供轉化塗層在金屬表面上，此轉化塗層極少受 隨後加熱及/或烘烤所影響。本發明的又一目的在提供用於 處理金屬表面之組成物和方法，特別是處理鋅、鋅合金、 鋁和鋁合金的表面。 發明槪沭 本發明的此等和其它目的可經由使用包含下列者之組成 物處理金屬表面予以達到： (1) 鎢酸鹽離子源；及 (2) 含鍩之可溶性物質；及然後乾燥或烘烤此等金屬表 面。 本發明特別適合於處理鋅和鋅合金表面以及鋁和鋁合金 200303934 的表面。本發明人發現：最好將處理組成物的 到2.0至7.0間。該處理組成物宜不含鉻離子 (四）實施方式： 發明之詳細說明 本文中發明人建議一種組成物及使用包含下 成物處理金屬表面之方法； (1 )鎢酸鹽離子源；及 (2)含鍩之可溶性物質；及然後乾燥或烘烤 面。 鎢酸鹽離子源包括所有之鎢酸鹽，但是最特 鎢酸鹽、偏鎢酸鹽及仲鎢酸鹽、聚鎢酸鹽、雜 異聚鎢酸鹽、過氧鎢酸鹽及其組合。以偏或對 源較佳。鎢酸鹽離子的適當來源包括鎢酸鈉、 、鈽、鋇、鎂、緦、氫和銨等鹽類，偏鎢酸銨 、偏鎢酸鈉、鎢酸、鎢酸鈉、鎢酸鉀和鎢酸銨 性鎢酸鹽，例如鎢酸銨或鉀供使用於液體濃縮 液兩者中最佳。組成物中鎢酸鹽的濃度（以鎢領 應爲約〇.〇lg/l至約l〇g/l，較佳約o.lg/l至約 最佳是約1 . 0 g /1。 該組成物亦包括含有鍩之可溶性化合物，較 。適當包含锆之物質的實例包括（但不限於）氟 氟銷酸二氫、六氟锆酸鉀、硫酸鍩、碳酸鍩、 酸锆。六氟銷酸二氫是最佳包含鍩之化合物。 锆之化合物的濃度其範圍較佳爲約0.0 1 g /1至 p Η値調節 列者之該組 此等金屬表 別是所有正 聚鎢酸鹽、 鎢酸鹽的來 鉀、鋰、鈣 、偏鎢酸鉀 。一種可溶 物及處理溶 11量）其範圍 1.5 g/Ι，而 佳爲氟化物 化銨銷、六 硝酸锆和磷 組成物中含 5 2.0g/l，更 200303934 佳爲約0.0 5 g /1至約〇 . 5 g /1。 本案發明人判定：較佳爲應將處理組成物的P H値維持 在約2.0至約7 · 〇，更佳在2 · 8至7 · 0。本案發明人發現： 當在前述範圍（2 . 〇 - 7.0 )以外操作時，所提供之腐蝕保護實 質上較差，且ρ Η値在較佳範圍以外之處理組成物水溶液 的穩定性比所需要者較低。 處理浴宜包括氫氧化銨作爲濃縮物及自該濃縮物所造成 之處理溶液的中和劑。爲了調節液體濃縮物的ρ Η値至高 pH値以便該濃縮物不會變得不穩定，必須有氫氧化銨。 ® 本案發明人亦已發現：處理組成物中鋁的集結，當與新 成形浴比較，可增加該浴產生優良抗腐蝕性之能力。在已 在舊處理浴中所處理之面板上，本案發明人實現1，0 0 0小 時的抗鹽水噴霧性。 爲該目的，可將一種可溶性鋁鹽加到本發明的處理組成 物中。可使用於本發明中之可溶性鋁鹽包括氯化銨鋁、硫 酸銨鋁、硝酸鋁、硫酸鉀鋁及硫酸鋁。如果使用的話，該 φ 鋁鹽通常應以5至5 0 0 ppm之濃度（作爲鋁）存在於該浴中， 而較佳之濃度係在1 0至2 Ο Ο ρ p m間（作爲鋁）。 一般，將使用本發明的組成物所處理之零件淸潔並移除 污物及其它表面污染。然後宜將零件在酸性溶液中去氧化 ，其能移除表面氧化物，然後沖洗。用於鍛合金之適當酸 性溶液是5 0 %硝酸溶液，惟亦可使用其它酸性溶液。然後 經由浸漬或經由噴灑，使零件與本發明的鎢酸銷組成物接 觸歷約3 0秒至約1 〇分鐘之時間。較佳爲將處理組成物維 -9- 200303934 持在範圍約5 5 °F至約1 8 0 °F之溫度下，最佳約7 0 °F至約1 2 0Τ 。然後，在塗刷或其它處理前，將零件乾燥及/或烘烤。 可將視需要之成分加至該處理組成物中，包括界面活性 劑、加速劑、染料、有機聚合物、緩衝劑和pH調節劑。 以下列實例來更進一步說明本發明。應將其採用僅作爲 舉例說明而非以任何理由限制本發明。 實例1 : 首先將金屬零件浸泡在1 7 0 °F之鹼性淸潔溶液中歷1 0至 1 5分鐘予以淸洗而移除金屬零件的表面污染。此實例中， ® 所使用之鹼性淸潔溶液是MacDermid TS 40 A，其濃度是 6 oz/gal，惟亦可使用其它鹼性淸潔溶液。其次，將零件沖 洗歷大約2分鐘的時間。將零件在周圍溫度下於5 0 %硝酸 溶液中去氧化（反應）歷大約1分鐘的時間，然後使其經歷 二次沖洗。將零件在室溫至約1 2 5 °F之溫度下經歷本發明 的轉化塗料歷約2至1 0分鐘時間。然後將零件沖洗歷最後 時間並予以乾燥及/或烘烤。最後，可將零件塗覆或作其它 φ 情況處理。表1提供可使用於本發明中之加工浴濃度的溶 液之數個實例。 表1本發明的溶液之適當浴濃度 成分 配方A 配方B 配方C 鎢酸、六銨鹽 3 . Og/1 2.5g/l 3 .5g/l 六氟鍩酸二氫 3.〇g/l 2.5g/l 3.5g/l 水 稀釋至1升 稀釋至1升 稀釋至1升 -10- 200303934 實例2 : 對於在實施例1之組成物中浸漬5分鐘而處理的面板， 調查熱處理對於中性鹽噴灑試驗結果的影響。此係藉由在 各不同的溫度烘烤樣品面板各1 〇分鐘，及比較經鉻酸鹽轉 化塗料所塗覆的面板之結果。結果示於表2中。 表2 :就鎢酸銷塗料及鉻酸鹽塗料，比較熱處理對於中 性鹽噴灑試驗結果的影響 溫度，°c 失效前之小時 鎢酸鉻塗料 鉻酸鹽塗料 15 0 1 6 8小時 <24小時 200 1 4 4小時 <24小時 2 5 0 1 4 4小時 <24小時 3 0 0 3 1 2小時 <24小時 3 5 0 3 1 2小時 <24小時 如可容易得知’在高溫下，使用本發明的組成物所處理 之面板較使用鉻酸鹽轉化塗料所塗覆之相似面板提供大很 多的腐蝕保護。 實例3 ： 依照MIL-C- 8 1 7 0 6和MIL-C- 5 5 4 1將使用鍩和鎢溶液所 處理之面板與使用絡酸鹽轉化塗料所處理之面板並列試驗 。爲了作比較’將裸鋁面板包括入該試驗中。將經過處理 (或裸錦）之面板使用底漆及/或塗料噴灑或予以粉末塗覆 。然後依照ASTM(美國材料試驗學會）d 3 3 5 9 _87, B方法 (使用膠帶用以量測黏著之標準試驗方法），使經過處理（或 200303934 裸鋁）之面板歷經2毫米網狀/膠帶扯離試驗。如所預測， 裸鋁面板產生一致的黏著失效。在另一方面，以鎢酸鉻塗 覆之面板提供等於或超過以鉻酸鹽塗覆之面板者的黏著促 進。 實例4 : 其次，將本發明的以鎢酸锆塗覆之面板與使用MIL-C. 8 1 7 0 6 / Μ I L - C - 5 3 4 1鉻酸鹽處理之面板並列試驗，爲了作比 較，使用裸鋁面板（在將此等面板在高溫下加熱或烘烤以後）。 此實例中，在上漆前將經過處理（或裸鋁）之面板加熱至 1 5 0 °C、2 0 0 °C、2 5 0 °C、3 0 0 °C 和 3 5 0 t 的溫度歷 2 0 分鐘時 間。經過處理（或裸鋁）之面板使用底漆予以噴塗，然後上 漆。 然後依照ASTM D 3 3 5 9 - 8 7 B方法使各面板歷經2毫米網 狀/膠帶扯離試驗。結果顯示：以鎢酸鉻處理之面板的黏著 促進遠超過裸鋁面板或以鉻酸鹽處理之面板的黏著促進。200303934 发明 Description of the invention (The description of the invention should state: the technical field, prior art, content, embodiments, and drawings of the invention are briefly explained)-(1) the technical field to which the invention belongs: The present invention relates to Composition and method of layer on metal surface. The conversion coatings of the present invention are generally chromium-free and can improve the corrosion resistance of treated surfaces and the adhesion of dry organic finishes to those treated surfaces. In addition, the conversion coating of the present invention is rarely affected by subsequent heating and / or baking steps. The invention can be used for the treatment of steel and other metals, but is particularly suitable for the treatment of zinc, zinc alloys, aluminum and aluminum alloys. φ (2) Prior technology: In order to form a coating to protect the metal from corrosion and to improve the adhesion of the subsequently applied dry organic finish, various conversion coatings suitable for metal surfaces have been suggested in previous techniques. These conversion coatings are produced by treating a metal surface with a solution of various chemicals, and these chemical solutions react with the surface to form a desired coating. Common conversion coating compositions typically include phosphates and chromates. Phosphate conversion coatings, especially on steel, have been used for a long time. The simplest phosphate solution includes an aqueous solution of an alkali metal phosphate which can react with iron, aluminum and / or zinc to form a phosphate conversion coating. Although in many applications, phosphate conversion coatings can increase the corrosion resistance of treated surfaces and the adhesion of dry organic finishes that are subsequently applied, better results are needed. Chromate conversion coatings generally provide much better corrosion resistance and adhesion than phosphate coatings. However, chromate conversion coatings do not provide good -6- 200303934 good corrosion resistance and adhesion at high temperatures. Chromate solutions typically include an aqueous solution of hexavalent and / or trivalent chromium and other additives. Historically, octavalent chromium has produced the best performance chromate conversion coatings. However, recent improvements in the 'divalent chromate technology have allowed trivalent chromate to compete with hexavalent chromate in performance. Typical chromate compositions and methods of making the same are disclosed in U.S. Patent Nos. 5,05,07,7,4,9 and 4,3,4,9,9,2, the teachings of which are incorporated herein by for reference. In any case, chromium has been identified as a fairly toxic metal and is strictly regulated. As a result, great efforts have been made to replace chromate paints with chromium-free paints. (3) Summary of the Invention: Therefore, the object of the present invention is to provide a composition and method capable of generating a conversion coating on a metal surface. The coating can provide excellent corrosion resistance and adhesion to dry organic finishes, and No chromium content. In addition, an object of the present invention is to provide a conversion coating on a metal surface, which conversion coating is rarely affected by subsequent heating and / or baking. Still another object of the present invention is to provide a composition and a method for treating a metal surface, particularly a surface of zinc, a zinc alloy, aluminum, and an aluminum alloy. Invention 槪 沭 These and other objects of the present invention can be achieved by treating metal surfaces with a composition comprising: (1) a source of tungstate ions; and (2) soluble substances containing rhenium; and then dried or baked Bake these metal surfaces. The invention is particularly suitable for treating the surfaces of zinc and zinc alloys as well as the surfaces of aluminum and aluminum alloys 200303934. The inventors have found that it is preferable to treat the composition to between 2.0 and 7.0. The treatment composition preferably does not contain chromium ions. (4) Embodiments: Detailed description of the invention The inventor herein proposes a composition and a method for treating a metal surface using the inclusions; (1) a tungstate ion source; and ( 2) Soluble substances containing rhenium; and then drying or baking the noodles. Tungstate sources include all tungstates, but most specific tungstates, metatungstates and paratungstates, polytungstates, heteropolytungstates, peroxotungstates, and combinations thereof. It is better to bias or to the source. Suitable sources of tungstate ions include salts such as sodium tungstate, osmium, barium, magnesium, rhenium, hydrogen and ammonium, ammonium metatungstate, sodium metatungstate, tungstic acid, sodium tungstate, potassium tungstate, and tungsten Ammonium tungstates such as ammonium tungstate or potassium are best used in both liquid concentrates. The concentration of tungstate in the composition (about 0.1 g / l to about 10 g / l, preferably about 0.1 g / l to about 10 g / l with a tungsten collar) is about 1.0 g / 1. The composition also includes soluble compounds containing hafnium, and examples of materials that suitably contain zirconium include, but are not limited to, difluorofluorohydrogen dihydrogen, potassium hexafluorozirconate, hafnium sulfate, hafnium carbonate, zirconium acid. Hexafluoro Dihydrogen acid is the most preferred compound containing hafnium. The concentration of the zirconium compound is preferably in the range of about 0.0 1 g / 1 to p. The group of those who are regulated by this group of metals is all orthopolytungstates , Potassium, lithium, calcium, potassium metatungstate of a tungstate. A soluble substance and a processing amount of 11) its range is 1.5 g / 1, and preferably ammonium fluoride pin, zirconium hexanitrate and phosphorus composition It contains 5 2.0 g / l, more preferably 200303934, and preferably about 0.0 5 g / 1 to about 0.5 g / 1. The inventor of the present case determined that it is preferred that the pH of the treatment composition should be maintained at about 2.0 to about 7.0, and more preferably at about 2.8 to 7.0. The inventors of the present case have found that when operating outside the aforementioned range (2.0-7.0), the corrosion protection provided is substantially poor, and the stability of the aqueous solution of the treatment composition outside the preferred range is greater than required Lower. The treatment bath preferably includes ammonium hydroxide as a concentrate and a neutralizing agent for the treatment solution resulting from the concentrate. In order to adjust the pH of the liquid concentrate to a high pH so that the concentrate does not become unstable, ammonium hydroxide is necessary. ® The inventors of this case have also discovered that the agglomeration of aluminum in the treatment composition, when compared with a new forming bath, can increase the bath's ability to produce excellent corrosion resistance. On the panel which has been treated in the old treatment bath, the inventors of the present invention achieved a salt spray resistance of 1,000 hours. For this purpose, a soluble aluminum salt may be added to the treatment composition of the present invention. Soluble aluminum salts that can be used in the present invention include ammonium aluminum chloride, aluminum ammonium sulfate, aluminum nitrate, potassium aluminum sulfate, and aluminum sulfate. If used, the φ aluminum salt should generally be present in the bath at a concentration of 5 to 500 ppm (as aluminum), and a preferred concentration is between 10 and 2 0 ρ p m (as aluminum). Generally, parts treated with the composition of the present invention are cleaned and removed with dirt and other surface contamination. The parts should then be deoxidized in an acidic solution, which can remove surface oxides and then rinse. A suitable acidic solution for wrought alloys is a 50% nitric acid solution, but other acidic solutions can also be used. The parts are then contacted with the tungstic acid pin composition of the present invention for a period of about 30 seconds to about 10 minutes by dipping or spraying. It is preferred to maintain the treatment composition dimension -9-200303934 at a temperature ranging from about 55 ° F to about 180 ° F, most preferably from about 70 ° F to about 120 ° T. The parts are then dried and / or baked prior to painting or other processing. If necessary, ingredients may be added to the treatment composition, including a surfactant, an accelerator, a dye, an organic polymer, a buffer, and a pH adjuster. The following examples further illustrate the present invention. It should be adopted only as an illustration and not to limit the invention for any reason. Example 1: First immerse metal parts in alkaline cleaning solution at 170 ° F for 10 to 15 minutes and rinse them to remove the surface contamination of the metal parts. In this example, the alkaline cleaning solution used by ® is MacDermid TS 40 A. Its concentration is 6 oz / gal, but other alkaline cleaning solutions can also be used. Second, rinse the parts for about 2 minutes. The parts were deoxidized (reacted) in a 50% nitric acid solution at ambient temperature for approximately 1 minute, and then subjected to a second rinse. The part is subjected to the conversion coating of the present invention at a temperature of from room temperature to about 125 ° F for a period of about 2 to 10 minutes. The parts are then rinsed for the final time and dried and / or baked. Finally, the part can be coated or otherwise treated. Table 1 provides several examples of solutions that can be used in the processing bath concentrations of the present invention. Table 1 Appropriate bath concentration ingredients of the solution of the present invention Formula A Formula B Formula C Tungstic acid, hexaammonium salt 3.0 Og / 1 2.5g / l 3.5 G / l hexafluorophosphonic acid dihydrogen 3.0 g / l 2.5 g / l 3.5g / l diluted with water to 1 liter diluted to 1 liter diluted to 1 liter -10- 200303934 Example 2: For panels treated by immersing in the composition of Example 5 for 5 minutes, investigate heat treatment for neutral salts Impact of spray test results. This is done by baking the sample panels for 10 minutes at different temperatures and comparing the results of panels coated with chromate conversion coatings. The results are shown in Table 2. Table 2: For tungstic acid coatings and chromate coatings, compare the effect of heat treatment on the results of the neutral salt spray test temperature, ° c hour before the failure of chromium tungstate coatings chromate coating 15 0 1 6 8 hours < 24 Hours 200 1 4 4 hours < 24 hours 2 5 0 1 4 4 hours < 24 hours 3 0 0 3 1 2 hours < 24 hours 3 5 0 3 1 2 hours < 24 hours At high temperatures, panels treated with the composition of the invention provide much greater corrosion protection than similar panels coated with chromate conversion coatings. Example 3: The panels treated with thorium and tungsten solutions and the panels treated with complexate conversion coatings were tested side by side in accordance with MIL-C-8 1 7 0 6 and MIL-C- 5 5 4 1. For comparison ', a bare aluminum panel was included in the test. Spray or powder coat treated (or bare) panels with a primer and / or paint. Then according to ASTM (American Society for Testing and Materials) d 3 3 5 9 _87, B (standard test method using adhesive tape to measure adhesion), the treated (or 200303934 bare aluminum) panel is subjected to a 2 mm mesh / tape Tear off test. As expected, bare aluminum panels produced consistent adhesion failures. On the other hand, a panel coated with chromium tungstate provides an adhesion promotion equal to or more than that of a panel coated with chromate. Example 4: Next, a side-by-side test of a panel coated with zirconium tungstate of the present invention and a panel treated with MIL-C. 8 1 7 0 6 / M IL-C-5 3 4 1 chromate was performed for comparison. , Use bare aluminum panels (after heating or baking these panels at high temperature). In this example, the treated (or bare aluminum) panel is heated to a temperature of 150 ° C, 20 ° C, 250 ° C, 300 ° C, and 350 ° C before painting. Over 20 minutes. The treated (or bare aluminum) panels are sprayed with a primer and then painted. Each panel was then subjected to a 2 mm mesh / tape peel test in accordance with ASTM D 3 3 5 9-8 7 B. The results show that the adhesion promotion of the panel treated with chromium tungstate is far more than that of bare aluminum panel or the panel treated with chromate.

Claims (1)

200303934 拾、申請專利範圍 1 . 一種形成在轉化層在金屬表面上之方法，包括下列步驟： 使用包含下列者之水性處理溶液處理金屬表面； (1) 鎢酸鹽離子源；及 (2) 含銷之可溶性物質；並 然後將經處理之金屬表面乾燥及/或烘烤。 2 .如申請專利範圍第1項之方法，其中該水性處理溶液更 含有氫氧化銨。200303934 Patent application scope 1. A method for forming a conversion layer on a metal surface, comprising the following steps: treating the metal surface with an aqueous treatment solution containing: (1) a tungstate ion source; and (2) containing Soluble materials; and then the treated metal surface is dried and / or baked. 2. The method according to item 1 of the patent application scope, wherein the aqueous treatment solution further contains ammonium hydroxide. 3 .如申請專利範圍第1項之方法，其中鎢酸鹽離子源係選 i 自下列所構成之族群：正鎢酸鹽、偏鎢酸鹽和仲鎢酸鹽 、聚鎢酸鹽、雜聚鎢酸鹽、異聚鎢酸鹽、過氧鎢酸鹽及 其組合物。 4 .如申請專利範圍第3項之方法，其中鎢酸鹽離子源是偏 鎢酸鹽或仲鎢酸鹽。 5 .如申請專利範圍第3項之方法，其中鎢酸鹽離子源係選 自下列所構成之族群：鈉、鉀、鋰、鈣、鈽、鋇、鎂、 H 緦、氫及銨之鎢酸鹽。 6 .如申請專利範圍第3項之方法，其中鎢酸鹽離子源是鎢 酸、六銨鹽。 7 .如申請專利範圍第1項之方法，其中處理溶液中以鎢測 量之鎢酸鹽離子的濃度是約〇.〇1 g/Ι至約1〇.〇 g/Ι。 8 .如申請專利範圍第7項之方法，其中處理溶液中以鎢測 量之鎢酸鹽離子的濃度是約〇.lg/l至約1.5g/l。 9 .如申請專利範圍第8項之方法，其中處理溶液中以鎢測 -13- 200303934 量之鎢酸鹽離子的濃度是l.o gn。 1 〇 .如申請專利範圍第1項之方法，其中含鍩之可溶性物質 係選自下列所構成之族群：氟化銨锆、六氟銷酸二氫、 六氟锆酸鉀、硫酸鍩、碳酸锆、硝酸銷和磷酸锆。 1 1 .如申請專利範圍第1 〇項之方法，其中含锆之可溶性物 質是六氟锆酸二氫。 1 2 .如申請專利範圍第1項之方法，其中處理溶液中的含锆 之可溶性物質的濃度是約〇.〇lg/l至約2.0g/l。 1 3 .如申請專利範圍第1 2項之方法，其中處理溶液中的含 鉻之可溶性物質的濃度是約〇.〇5 g/Ι至約0.5 g/Ι。 1 4 .如申請專利範圍第1項之方法，其中水性處理溶液更包 含一種可溶性鋁鹽。 1 5 .如申請專利範圍第1 4項之方法，其中可溶性鋁鹽的濃 度以鋁計算係在5至5 0 0 p p m間。 1 6 .如申請專利範圍第1項之方法，其中處理溶液的溫度係 在約5 5 °F至約1 8 0 °F之範圍內。 1 7 .如申請專利範圍第1 6項之方法，其中處理溶液的溫度 係在約7 0 °F至約1 2 0 °F。 1 8 .如申請專利範圍第1項之方法，其中該處理溶液的p Η 値係維持在約2.8至約7.0。 1 9 .如申請專利範圍第1項之方法，其中在使用處理溶液處 理金屬表面前，將零件淸潔。 2 0 .如申請專利範圍第1 9項之方法，其中在淸潔後及在使 用處理溶液處理前，將金屬表面去氧化。 -14- 200303934 2 1 .如申請專利範圍第1項之方法，其中處理溶液不含絡。 2 2 .如申請專利範圍第1項之方法，其中處理溶液係經由浸 漬或經由噴灑而施加。 2 3 .如申請專利範圍第1項之方法，其中處理溶液更包含至 少一種界面活性劑、加速劑、染料、有機聚合物、緩衝 劑和P Η調節劑。 2 4 . —種水性轉化塗料組成物，包括鎢酸鹽離子源及包含銷 之可溶性物質。 2 5 .如申請專利範圍第2 4項之組成物，其中水性處理溶液 更包含氫氧化銨。 2 6 .如申請專利範圍第2 4項之組成物，其中鎢酸鹽離子源 係選自下列所構成之族群：正鎢酸鹽、偏鎢酸鹽和仲鎢 酸鹽、聚鎢酸鹽、雜聚鎢酸鹽、異聚鎢酸鹽、過氧鎢酸 鹽及其組合物。 2 7 .如申請專利範圍第2 6項之組成物，其中鎢酸鹽離子源 是偏鎢酸鹽或仲鎢酸鹽。 2 8 .如申請專利範圍第2 6項之組成物，其中鎢酸鹽離子源 係選自下列所構成之族群：鈉、鉀、鋰、鈣、鈽、鋇、 鎂、總、氣及銨之鎢酸鹽。 2 9 .如申請專利範圍第2 6項之組成物，其中鎢酸鹽離子源 是鎢酸、六銨鹽。 3 0 .如申請專利範圍第2 4項之組成物，其中處理溶液中以 鎢測量之鎢酸鹽離子的濃度是約〇.〇lg/l至約l〇.〇g/l。 3 1 .如申請專利範圍第3 0項之組成物，其中處理溶液中以 鎢測量之鎢酸鹽離子的濃度是約0.1 g/Ι至約1.5 g/Ι。 -15- 200303934 % 3 2 .如申請專利範圍第3 1項之組成物，其中處理溶液中以 鎢測量之鎢酸鹽離子的濃度是1 .〇g/l。 3 3 .如申請專利範圍第2 4項之組成物，其中含锆之可溶性 物質係選自下列所構成之族群：氟化銨锆、六氟鉻酸二 氫、六氟锆酸鉀、硫酸銷、碳酸锆、硝酸锆和磷酸鍩。 3 4 .如申請專利範圍第3 3項之組成物，其中含锆之可溶性 物質是六氟鍩酸二氫。3. The method according to item 1 of the scope of patent application, wherein the tungstate ion source is selected from the group consisting of orthotungstate, metatungstate and paratungstate, polytungstate, heteropolymer Tungstate, isopolytungstate, peroxotungstate and combinations thereof. 4. The method of claim 3, wherein the source of the tungstate ion is metatungstate or paratungstate. 5. The method of claim 3, wherein the tungstate source is selected from the group consisting of sodium, potassium, lithium, calcium, thallium, barium, magnesium, H thorium, hydrogen, and ammonium tungstic acid salt. 6. The method of claim 3, wherein the source of tungstate is tungstic acid and hexaammonium salt. 7. The method according to item 1 of the patent application range, wherein the concentration of the tungstate ion measured by tungsten in the treatment solution is from about 0.01 g / 1 to about 10.0 g / 1. 8. The method according to item 7 of the patent application range, wherein the concentration of the tungstate ion measured by tungsten in the treatment solution is about 0.1 g / l to about 1.5 g / l. 9. The method according to item 8 of the scope of patent application, wherein the concentration of the tungstate ion measured in tungsten in the processing solution is -13-200303934, which is l.o gn. 10. The method according to item 1 of the scope of patent application, wherein the soluble material containing thorium is selected from the group consisting of ammonium zirconium fluoride, hexafluorohydrogen dihydrogen, potassium hexafluorozirconate, thorium sulfate, carbonate Zirconium, nitrate pins and zirconium phosphate. 11. The method of claim 10 in the scope of the patent application, wherein the soluble substance containing zirconium is dihydrohexazirconate dihydrogen. 12. The method according to item 1 of the patent application range, wherein the concentration of the zirconium-containing soluble substance in the treatment solution is from about 0.00g / l to about 2.0g / l. 13. The method according to item 12 of the scope of patent application, wherein the concentration of the soluble substance containing chromium in the treatment solution is from about 0.05 g / l to about 0.5 g / l. 14. The method according to item 1 of the patent application range, wherein the aqueous treatment solution further comprises a soluble aluminum salt. 15. The method according to item 14 of the scope of patent application, wherein the concentration of the soluble aluminum salt is in the range of 5 to 500 p p m in terms of aluminum. 16. The method according to item 1 of the patent application range, wherein the temperature of the treatment solution is in a range of about 55 ° F to about 180 ° F. 17. The method according to item 16 of the patent application range, wherein the temperature of the treatment solution is from about 70 ° F to about 120 ° F. 18. The method according to item 1 of the patent application range, wherein the p Η 値 of the treatment solution is maintained at about 2.8 to about 7.0. 19. The method according to item 1 of the scope of patent application, wherein the part is cleaned before the metal surface is treated with the treatment solution. 20. The method according to item 19 of the scope of patent application, wherein the metal surface is deoxidized after cleaning and before treatment with a treatment solution. -14- 200303934 2 1. The method according to item 1 of the scope of patent application, wherein the treatment solution does not contain sulfonium. 2 2. The method of claim 1 in which the treatment solution is applied by dipping or spraying. 2 3. The method according to item 1 of the patent application range, wherein the treatment solution further comprises at least one surfactant, accelerator, dye, organic polymer, buffer, and PP regulator. 2 4. A water-based conversion coating composition including a source of tungstate ion and a soluble substance containing a pin. 25. The composition as claimed in claim 24, wherein the aqueous treatment solution further comprises ammonium hydroxide. 2 6. The composition according to item 24 of the scope of patent application, wherein the source of tungstate is selected from the group consisting of orthotungstate, metatungstate and paratungstate, polytungstate, Heteropolytungstate, isopolytungstate, peroxotungstate and combinations thereof. 27. The composition according to item 26 of the patent application, wherein the source of the tungstate ion is metatungstate or paratungstate. 28. The composition according to item 26 of the scope of patent application, wherein the source of tungstate is selected from the group consisting of sodium, potassium, lithium, calcium, thallium, barium, magnesium, total, gas, and ammonium. Tungstate. 29. The composition according to item 26 of the patent application scope, wherein the tungstate ion source is tungstic acid and hexaammonium salt. 30. The composition according to item 24 of the scope of patent application, wherein the concentration of the tungstate ion measured by tungsten in the treatment solution is from about 0.00g / l to about 10.0g / l. 31. The composition of claim 30, wherein the concentration of the tungstate ion measured in tungsten in the treatment solution is about 0.1 g / l to about 1.5 g / l. -15- 200303934% 3 2. The composition according to item 31 of the scope of patent application, wherein the concentration of the tungstate ion measured by tungsten in the treatment solution is 1.0 g / l. 3 3. The composition according to item 24 of the scope of patent application, wherein the soluble substance containing zirconium is selected from the group consisting of ammonium zirconium fluoride, dihydrogen hexafluorochromate, potassium hexafluorozirconate, and sulfate , Zirconium carbonate, zirconium nitrate and hafnium phosphate. 34. The composition according to item 33 of the scope of patent application, wherein the soluble substance containing zirconium is dihydrohexafluoroarsinate. 3 5 .如申請專利範圍第2 4項之組成物，其中處理溶液中的 含锆之可溶性物質的濃度是約〇.〇1 g/Ι至約2.0 g/Ι。 3 6 .如申請專利範圍第3 5項之組成物，其中處理溶液中的 含锆之可溶性物質的濃度是約〇.〇5 g/Ι至約0.5 g/Ι。 3 7 .如申請專利範圍第2 4項之組成物，其中水性處理溶液更 包含一種可溶性鋁鹽。 3 8 .如申請專利範圍第3 7項之組成物，其中可溶性鋁鹽的濃 度以鋁計算係在5至5 0 0 p p m間。 3 9 .如申請專利範圍第2 4項之組成物，其中處理溶液之溫度35. The composition according to item 24 of the scope of patent application, wherein the concentration of the zirconium-containing soluble substance in the treatment solution is from about 0.01 g / 1 to about 2.0 g / 1. 36. The composition of claim 35, wherein the concentration of the zirconium-containing soluble substance in the treatment solution is from about 0.05 g / l to about 0.5 g / l. 37. The composition as claimed in claim 24, wherein the aqueous treatment solution further comprises a soluble aluminum salt. 38. The composition according to item 37 of the scope of patent application, wherein the concentration of the soluble aluminum salt is in the range of 5 to 500 p p m in terms of aluminum. 39. The composition as claimed in item 24 of the patent application scope, wherein the temperature of the processing solution 係在約5 5 °F至約1 8 0 °F之範圍內。 4 0 .如申請專利範圍第3 9項之組成物，其中處理溶液之溫度 係在約7 0 °F至約1 2 0 °F。 4 1 .如申請專利範圍第2 4項之組成物，其中處理溶液之p Η 値係維持在約2.8至約7.0之間。 42 .如申請專利範圍第24項之組成物，其中處理溶液不含鉻。 4 3 .如申請專利範圍第2 4項之組成物，其中處理溶液更包 括至少一種界面活性劑、加速劑、染料、有機聚合物、 緩衝劑和Ρ Η調節劑。 -16- 200303934 陸、（一）、本案指定代表圖爲：第_圖 (二）、本代表圖之元件代表符號簡單說明: 柒、本案若有化學式時，請揭示最能顯示發明特徵的化學式:It is in the range of about 5 5 ° F to about 180 ° F. 40. The composition according to item 39 of the patent application range, wherein the temperature of the treatment solution is from about 70 ° F to about 120 ° F. 41. The composition according to item 24 of the scope of patent application, wherein p Η 处理 of the treatment solution is maintained between about 2.8 and about 7.0. 42. The composition of claim 24, wherein the treatment solution does not contain chromium. 43. The composition according to item 24 of the patent application scope, wherein the treatment solution further comprises at least one surfactant, accelerator, dye, organic polymer, buffer, and pH modifier. -16- 200303934 Lu, (a), the designated representative of the case is: Figure _ (b), the representative symbols of the representative illustration of the element: 柒, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention :
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