TWI374198B - - Google Patents
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- TWI374198B TWI374198B TW096114036A TW96114036A TWI374198B TW I374198 B TWI374198 B TW I374198B TW 096114036 A TW096114036 A TW 096114036A TW 96114036 A TW96114036 A TW 96114036A TW I374198 B TWI374198 B TW I374198B
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- plated steel
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/1266—O, S, or organic compound in metal component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12819—Group VB metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12937—Co- or Ni-base component next to Fe-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
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- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
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Description
修正日期:100.7.20 第96114036號專利申請案說明書修正本 九、發明說明: 【發明所屬之技術領域】 發明領域 本發明係一種未塗裝或塗裝後使用之鍍敷鋼材,且有 關於一種賦與優異之耐蝕性、耐變黑性 '塗裝密著性及耐 鹼性之複合被膜處理鍍敷鋼材。更詳而言之,本發明係有 關於-種可賦與將含鋅鍍敷鋼作為素材之成型加工品、例 ^作為屋誠牆壁等之㈣構件、或者料車子、機械、 家電製品等構件使用之成型加工品,或賦與捲片優異之耐 餘性、耐變黑性、塗裝密著性及魏性之完全不含絡且經 複合被膜處理之含鋅鍍敷鋼材。 發明背景 且㈣含鋅鑛敷鋼材,鍍敷鋼材係藉由鍍敷層金屬材料 型有之高祕機能,而可廣泛制料建材、汽車、家電 等的齡。㈣,鍍敷耐巾,相从氣中所含之 =等的電《、高溫多《境下存在 <氧、水分而氧化 戸二白鏽產生腐蝕之現象…在高溫多濕下,在特定的 會產生聽鋼材看起來變黑之現象。任—種現象 組裝^起·層金肺料的劣化,且作為前述之各種製品 之品質、設計性之觀點來看也會有問題。 又’即㈣Μ後使⑽情灯,切因為氧或水分 =過而在«Τ之紐射,也會發相躲生成物的 或堆積而引起之塗膜剝離,在設計性、實用性上也會 1374198 第96114036號專利申請案說明書修正本 修正曰期:100.7.20 產生問題。 又,在鍍敷鋼材進行成型加工後,會使用顯示鹼性之 · 脫脂劑來洗淨。此種情況下,若對鹼不具有耐久性則會變 · 色,使用下會很早就開始腐蝕。 5 防止此種鍍敷鋼材之腐蝕或變黑、塗膜剝離之方法, 以往係使用使含有鉻酸-鉻酸鹽、磷酸-鉻酸鹽等之鉻之處理 液與锻敷鋼材的表面接觸之各種方法,進行表面處理。藉 此’可藉使一般稱為反應型鉻酸鹽被膜者形成於鍍敷鋼材 表面’避免前述問題。藉由該等處理所得之鉻酸鹽被膜係 · 10 以3價鉻為主體’特別是有毒的6價鉻之溶出少者也不能說 . 完全具有防蝕性,特別是到加工或在深達肥粒鐵之裂痕等 所致使被膜損傷大時,鍍敷鋼材的耐蝕性會降低。 _ 另一方面’將含有6價鉻之處理液以輥塗方式塗布於素 - 材,乾燥所得之塗布型鉻酸鹽處理,在形成之被膜中含有 ‘ 15多量之6價鉻。因此,即使鉻酸鹽被膜受到加工或裂痕等致 使之損傷’會由具有優異之耐蝕性之反面、鉻酸鹽被膜溶 出6價鉻。含有6價鉻之鉻酸鹽處理被膜其毒性積存於人體 鲁 時會有不良影響,如先前所述,由於具有被膜溶出容易之 性質’因此環境負荷物質移動到系統外,由環境保全的觀 20 點來看會有問題。 如此,以往為防止白鏽產生於鍍敷鋼材施行之鉻酸鹽 處理其課題則是6價鉻對安全性、環境之影響。為了解決此 種問題,一直在研討替代鉻酸鹽處理之技術。 記載將不含有鉻酸鹽之處理液被覆於鍍敷鋼材表面之 6 絡酸鹽替代技術可舉日本專利公開公報特開2002_332574 為例。該刊彳T物中提its-種技術係藉將不含碳酸錯錯離子 與釩離子、一硫丁二酸等之處理液塗布、進行加熱乾燥, 形成緻密的3次元構造之被膜,且由於吸著於表面金屬之能 力高’因此雜性優異。又’日本翻公開公報特開2〇〇2 — 030460中,已舉出含有釩化合物、及由錯、鈦'鉬、鎢、 錳及鈽選出之至少1種金屬之化合物之金屬表面處理劑、金 屬表面處理金屬材料。又,在日本專利公開公報特開2〇〇4 —183015中’已舉出含有飢化合物、及含有姑锦、辞、 鎂、鋁等選出之至少1種金屬之金屬化合物之金屬表面處理 劑、金屬表面處理材料。 【發明内容:! 發明概要 然而,在任一種之鉻酸鹽替代技術中,在耐蝕性耐 變黑性及塗跋密著性上仍不足夠。此即為本發明欲解決之 課題。 發明者針對解決前述課題之方法專心檢討的結果,發 現使用含有特定組成之水溶液,處理含鋅鑛敷鋼材,可得 到具有優異之耐蝕性、耐變黑性、塗裝密著性及耐鹼性之 經複合被骐處理之含鋅鍍敷鋼材’終至完成本發明。 即’本發明係有關於一種具有優異之耐蝕性、耐變黑 性、塗裝密著性及耐鹼性之經複合被膜處理之含辞錢敷鋼 材,其特徵在於:具有一將含有驗性錯化合物、含飢(v 02+ )化合物、磷酸化合物、鈷化合物、有機酸及水之 1374198
第96114〇36號專利申請案說明書修正頁 ------------------------- 〜Η之處㈣塗布於錄㈣之表面,待乾驗形成之複 合被膜,該複合被膜中,相對於1〇〇質量%之^元素含有 比例為10〜45質量%之乂、5〜1〇〇質量%之?、〇 .卜扣 質量%之匸〇、10〜90質量%之有機酸。 5 本發明中,上述被膜之總被膜質量宜為50〜 2000mg/m2 ’ 100〜1500mg/m2在提昇耐蝕性 '耐變黑性、 塗裝密著性及耐驗性上特佳。
本發明之經複合被膜處理之含鋅鍍敷鋼材在耐蝕性、 Μ變黑性、塗裝密著性、耐驗性之任—者皆具有極為優異 Η)之性能,因此本發明係-在産業上具有極大意義之發明。' t實施方式:J 較佳實施例之詳細說明 本發明之複合被膜係由含有鹼性錯化合物、含釩 (V02+)化合物、磷酸化合物、鈷化合物、有機酸及水之 15 PH7〜14之處理液所形成。 鹼性錯化合物係用以供給複合被膜_之&元素之化合 物。鹼性鍅化合物沒有特別限定者,但可為例如具有陽離 子為〔Zr(C〇3)2(〇H)2〕2_ 或〔Zr(C〇3)3(〇H)〕3-之碳酸錯 化合物、或含有該等陽離子之銨鹽、鉀鹽、鈉鹽等。 20 含叙(VO2 )化合物係用以供給複合被膜中之V元素 之化合物。含釩(vo2+)化合物沒有特別限定,但可為如 氧-釩陽離子、與鹽酸、硝酸、磷酸、硫酸等無機酸陰離子 或蟻酸、醋酸、丙烯酸、正丁酸、草酸等之有機酸陰離子 之鹽。或者亦可使用如脲基乙酸釩、脫氫抗壞血酸釩之有 8 第96114036號專利申請案說明書修正本 修正曰期:100.7 2() 機酸與奴化合物之螯合物。 於複合被膜中,元素V相對於1〇〇質量,係含有 10〜45質量%。若V小於10質量%,則耐蝕性、耐鹼性可 能會降低。當V多於45質量%時,耐變黑性或塗裝密著性 會降低。複合被膜中之V量相對於1〇〇質量%之乙1·,宜為15 〜30質量%、更宜為2〇〜25質量%。 磷酸化合物係用以供給複合被膜中之P元素之化合 物。磷酸化合物沒有特別限定,但可為磷酸及其胺鹽等。 更具體而S,可舉如正填酸、焦碟酸、偏構酸、多碟酸、 植酸、膦酸、磷酸銨、磷酸二氫銨、磷酸氫二銨、磷酸鈉、 磷酸鉀等。 複合被膜中,元素P相對於100質量%之Zr,係含有5 〜100質量% ° P’j、於5質量%時,性會降低’多於1〇〇 質里時耐變黑性、塗膜密著性、对驗性會降低。複合 被膜中之P量相對於1〇〇質量%Zr,宜含有10〜70質量%、 更宜為1G〜4G質量% '最宜為12〜2G質量%。 結化合物係用以供給複合被膜中之Co元素之化合物。 鈷化合物並非有特別限定,亦可為例如、碳酸鈷硝酸鈷、 硫酸鈷、醋酸鈷等。 複合被膜中’含有相對於100質量%2Zr為0.1〜20質量 %之元素C。。當C。小於〇.1質量%時,㈣黑性會降低,當 Co多於2G ff:%時,咖性、耐鹼性、f卿著性會降低。 特另】是《«為姑的政果係可在被膜形成時促進鍍敷鋼材表面 的不活性化’且由水、氧等外在因素來看具有保護的作用。 1374198 第96114036號專利申請案說明書修正本 修正曰期:100.7.20 複合被膜中之Co的量係相對於1〇〇質量%之心、以含有〇 . 5 〜10質量%者為佳,以0 . 5〜5質量%者為較佳,以〇 . 8〜 1 · 5質量%者為特佳。 本發明之複合被膜中也含有有機酸。有機酸係含有如 5脲基乙酸、蘋果酸'酒石酸、草酸、檸檬酸、抗壞企酸、 乳酸、脫氫苯甲酸、脫氫抗壞血酸、没食子酸、丹寧酸、 植酸。也可根據情況使用該等之有機酸之銨鹽。 複合被膜中含有相對於1〇〇質量%2Zr為10〜90質量 %之有機酸。若有機酸相對於1〇〇質量,小於1〇質量 10 % ’則耐蝕性或塗裝密著性會略為劣化。又,處理液中有 機酸少時’處理液之保存性會降低。即,藉於有機酸形成 含釩(V02+)化合物、鹼性錯化合物、磷酸化合物與錯合 物’也具有可維持形成複合被膜之處理液(水溶液)之安 定性的效果。若相對於複合被膜中之10〇質量%之心,有機 15酸高於90質量%時,則塗裝密著性、耐鹼性會降低。複合 被膜中之有機酸的量以1〇〇質量%2Zr來計為1〇〜70質量 % ’以10〜5〇質量%為佳,尤以15〜30質量%為佳。 本發明之經複合被膜處理之含鋅鍍敷鋼材係在複合被 膜中,使用含有以上述比例供給Zr、V、P、Co元素及有 20機酸之量之鹼性錯化合物、含釩(vo2+)化合物、磷酸化 合物、鈷化合物'及有機酸之水溶液’於鍍敷鋼材的表面 塗布、加熱乾燥後,形成被膜而製成。 處理液宜為PH7〜14。在該pH範圍内,可使鹼性錯化 合物安定的溶化於水。處理液Ph值宜為8〜11,尤以8〜1〇 10 為佳。若必須調整處理液之PH值時,可使用如下所示之物 質作為pH調整劑。例如可舉,氨水、三乙胺、三乙醇胺、 磷酸 '硝酸、氟酸、碳酸、氟化銨等,pH調整劑若非可顯 著降低處理液安定性者則非特別限定。 形成之被膜係具有緻密的3次元構造,且為屏蔽性優 異,並可提升耐蝕性之複合被膜。形成該等複合被膜之其 中一個理由為,有機酸與金屬離子以形成錯合物進行錯 合,主要藉由Zr~ 〇形成緻密的三次元構造,於其間隙(網 目構造之間)混人V、有機酸、P、C。,再取得已利用鑛敷 表面之㈣取得之鋅。x ’藉由形成複合被糾之有機酸 之鍍敷表面的蝕刻,可增加被膜與鍍敷表面之間界面的密 著性,並提高耐姓性與塗裝密著性。 於表面形成有複合被膜之鍵敷鋼材只要係錄敷層含有 鋅即可,並無特職定。例如,亦可制具有由鋅與不可 避免之不麟構权魏層之職崎。或者,除了辞之 外(及不可避免之不純物),與辞之合金成分,亦可使用具 有3有A1 Mg、Si、Ti、Ni、Fe等鍍敷層之銀敷鋼材。最 好的鑛敷層除了鋅(及不可贼之不純物)之外還含有 6〇質量%以下之A1'10質量%以下之叫、2質量%以下之 Si之其中1種以上者。 鍍敷鋼材的魏層也可以任何—㈣敷法形成。例 如’鍍敷層亦可由熱錄 '電鍍、蒸鑛、散鍵、真空鍍敷法 等任-種方式形成。又,熱錢法有焊法、森吉来爾加化㈣ 法、或施行Ni等預鍍敷以確保浸濕性方法等,使用任一者 1374198 第96114036號專利申請案說明書修正頁 a ΜΗ : inn 〇 .. '~~ -:~~~~ 皆可。 又,要使鍍敷後之外觀變化,亦可於已鍍敷之鋼材喷 上水霧、氣水霧,或者喷上磷酸蘇打水溶液、亦可喷上鋅 粉、構酸鋅粉、鱗酸氫鎂粉末或該等之水溶液。 5 又,要再加強鍍敷之耐變黑性,亦可以在鍍敷後,進 行施行複合被膜處理之前處理,亦可施行使用硫酸鈷或硫 酸鎳溶液等之表面調整。 在鍍敷鋼材表面塗布處理液之塗布方法亦可使用喷霧 法、次潰法、輥塗法、淋浴法、氣刀法等任一種方法沒 10 有特別限定。 在塗布處理液時,亦可在不損及本來之性能的範圍内 添加活性劑或有機溶劑等,以提高對鍍敷鋼材之表面的濡 权性。又,亦可視需要添加消泡劑。 進而,可在處理液中添加潤滑劑或填充劑、例如二硫 15化鉬、石墨、二硫化鎢、氮化硼、氟化黑鉛、氟化鈽、三 1氰胺鼠酸鹽、氟素樹脂系蠛、聚醯烴系蠛、膠體二氧化 矽、氣相二氧化矽等,防止本發明之經複合被膜處理之含 鋅鍵敷鋼材在加工時有所損害或磨耗。 鍍敷鋼材表面之複合被膜的總被膜質量之範圍宜在50 20〜2000mg/m左右。在此範圍内,可得到本發明之目的之具 有良好的耐蝕性、耐變黑性、塗裝密著性及耐鹼性之經複 合被膜處理之含鋅鍍敷鋼材。複合被膜之特佳總被膜量範 圍為100〜1500mg/m2。小於100mg/m2時,耐蝕性、耐變黑 性、时驗性可會降低。若超過15〇〇mg/m2,則被膜會變脆 12 1374198 第96114036號專利申請案說明書修正本 修正日期:100.7.20 耐鹼性、塗裝密著性可能會降低。 使用處理液處理鍍敷鋼材時,宜以到達板溫在50°C〜 200°C之範圍加熱乾燥。又,加熱方法沒有特別限定者,熱 風、直火加熱、感應加熱、紅外線、電爐等任一種方法皆 5 可。 實施例 其次具體說明本發明,但本發明並不受限於以下具體例。 第1表係顯示製作出之複合被膜之Zr、V、P、Co及有 機酸的組成比。又,使用於處理液之化合物則如以下所示 10 之記號。
Zr : V : 15 P : 20 C〇 : 有機酸 A 1 :碳酸錯銨 A2 :碳酸錯鈉 A3 :碳酸锆鉀 B 1 :醋酸凯 B 2 :磷酸釩 B3 :擰檬酸釩 B4 :丙酸釩 C 1 :磷酸銨 C2 :磷酸鈉 D 1 :碳酸I古 D 2 :硝酸鈷 :E 1 :擰檬酸 E2 :順丁烯二酸 E3 :抗壞血酸 13 1374198 第96114036號專利中請案說明書修正本 修正日期:100.7.20 E4 :己二酸 又、比較條件使用了以下之習知技術。 習知技術1 : 由含有Zr、V、P,不含Co,並含有二硫丁二酸之處理 5 液所形成複合被膜。 習知技術2 : 由含有Zr、V,不含P、Co、有機酸之處理液所形成之 複合被膜。 習知技術3 : 10 由含有Zr、V、P、Co、有機酸,並且相對於100質量 %2Zr,V、有機酸的比例在本發明之範圍外之處理液 (V、有機酸任一者多)形成之複合被膜。 習知技術4 : 使用部分還元鉻酸水溶液(還元率40%)與膠體二氧 15 化石夕之混合液(Cr〇3 : Si〇2= 1 : 3)作為塗布型鉻酸鹽處 理液而形成之被膜。 20
複合被膜係使用報塗法,將成分以脫離子水希釋調整 出之預疋濃度之處理液塗布於鍵敷鋼材的表面,以得到預 定之乾燥被臈量,然後使用熱風乾燥機直接進行加熱浐 燥,使到達板溫為80°C而製成。處理液之Ph為9。 第2表係顯示製作出之試驗片的處理條件與試驗評俨 結果。使用之鍍敷鋼材由以下之記號表示之。 具 M1 :溶融鍍敷Zn (鍍敷付著量90g/m2) M2 :溶融鍍敷 11%A1_3%Mg 〇 · 办 14 1374198 第96114036號專利申請案說明書修正本 修正日期:100.7.20 (鍍敷付著量90g/m2) M3:電鍍Zn (鍍敷付著量2〇咖2) 綱:電鍍_士 (鍍敷付著量2— M5 :溶融鍍敷55%Al-U%Si_Zn 5 (錢敷付著量90g/m2) 以下顯示評價項目及試驗方法。 •而十姓性 對以施行平板及橫切加工之試驗片實施以瓜ζ 237ι 為依據之鹽水喷霧試驗個小時。耐餘性以鹽水喷霧試驗 10 後之白鏽發生面積率來判定。 耐蝕性之評價基準顯示如下。 平板試驗片: A 白鏽0% B 白鏽超過0%且在5%以下 15 C 白鏽超過5%且在30%以下 D 白鏽超過30% 橫切加工試驗片(包含剪切部及周邊的白鏽) A : 白鏽0% B : 白鏽超過0%且在5%以下 20 C : 白鏽超過5%且在30%以下 D : 白鏽超過30% •耐鹼性 使用 20g/L 之 palclean N 364 S ( NIHON Parkerizing (:〇.,1^0製)’將平板試驗片以進行60°(:且501^3之喷壓30秒 15 1374198 第96114036號專利申請案說明書修正本 修正曰期:100720 之喷霧處理,然後,以水管水洗淨10秒,使用冷風乾燥。 接著,如前述同樣實施鹽水喷霧試驗到240個小時,然後以 鹽水喷霧試驗後之白鏽發生面積率來加以判定。 耐驗性之評價基準顯示如下。 A :白鏽0% B :白鏽超過0%且在5%以下 C :白鏽超過5%且在30%以下 D :白鏽超過30% •耐變黑性 10 使用恆溫恆濕試驗,目視觀察在7{TCxRH85%的大氣 環境下,試驗片靜置144個小時後之外觀》 耐變黑性之評價基準顯示如下。 A :完全沒有變化 B :幾乎沒有變化 15 C :有些許變色 D :有明顯變色 •塗裝密著性 使用塗布棒將7 7夕1〇〇〇白(關西塗料社製)塗 布於試驗片上,以not加熱乾燥20分鐘後,得到20仁!^之 2〇 乾燥膜厚。接著,放入沸騰水中浸潰30分鐘,取出後自然 放置24小時。然後,使用剪刀進行1mm、100份之基板格子 加工’藉由膠帶剝離試驗求得塗膜殘存數。 塗裝密著性的評價基準顯示如下。 A :殘存數1〇〇個 16 1374198
第96114036號專利申請案說明書修正本 修正日期:100.7.20 B :殘存數在98個以上且小於100個 C :殘存數在50個以上且小於98個 D :殘存數小於50個 17 1374198 0ΖΖ.Ό01 :«BT#>4Ti^#ff^账·||«-^绛餚 9S 寸一 196 城 ί 1 柳月1 1 柳月I 1 柳月1 1 柳月1 1 柳月I 1 柳月1 1_柳月 I 1_柳月 I 丨柳月I 丨神月1 1 柳月I 丨紳月1 1 柳月1 L柳月1 1 柳月I 1 柳月1 1 柳月1 1_柳月1 1_ t 晒 I 1 t晒 I 1 t酬 I 1_ 瞻1 I L t晒 I 1 t賴 I 1 t晒 I 1 t晒 I 1 mm 1 1 tutm 1 1 t晒 1 tb♦崩 1 1 1 i 1 〇5 (二ζη*二«〇 ! 丨鉢·嫂 1 有麵 1 fft% 1 R R R Ο a s s s s s s s S s R U-) § 1 8 1 1 UJ UJ m ω UJ LU m UJ UJ UJ UJ UJ UJ UJ UJ a □ s UJ ULl UJ UJ UJ UJ UJ EX) LU 1 ω 6 質舰1 1 1 1 1 1 Q Q Q Q Q Q Q Q Q Q Q Q Q Q a o Q Q Q Q 〇 Q Q Q Q Q 1 1 s CU tm i jq in U-J 8 in jn jn JO jn jn »2 jo to »〇 JO JO f£i a § jn jn jn to s 1 00 1 1 O O U u U U u U U U U U υ 0 u u 〇 〇 U U u a a U U U u 1 U > 質舰1 o 夺 Ϊ0 s S S s S S S S S 8 S a s R S »〇 突 R S s S S S 突 8 1 1 CQ QQ CD CO CQ CQ CQ CD 0Q & 3 Si CQ 0Q CQ 0Q QQ CQ CQ 0Q 03 CQ CQ CD CQ QQ 00 ω rsl 質脱1 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 S 8 8 8 8 8 8 8 8 8 8 8 1 ib^sh 1 < < < < < < < < 5 < < < < < < < < < < < < < < < < < < < 複 I mm:\ i l I 1 1 I | I I I I 0 1 1 I 1 寸 1 Vi 1 v〇 1 卜 1 00 1 G\ I 1 1 1 1 1 1 1 複*M®G6 | 1習細挪 I 1習知}挪 1 1習細挪Ί 1習知}_ 1 1374198 £3.8.001 :琛给_ 17#|#丨器軺帐#|务眾|^95寸1196浓
蜞龙孥&z< I 1 I I ! 1 1 1 1 1 I ί I I 1 I 1 t 1 I 1 1 E £ 1 I Έ) 芬 1 1 I 1 1 I ΛΧ i ΛΛ Έ 署 I 1 I 1 I l I i 魏錄11 1________ < < < < < < < < < < < < < < < < < < < < < < < < < CQ < < < 02 02 U CQ 〇 CQ u u CJ u u CJ CQ 概R性 1______ < < < < < < < < < < < < < < < < < < < < < < CQ < < < CQ < < < CQ U CD a Q CQ ω CQ Q Q Q L) 1 1 < < < < < < < < < < < < < < < < < < < < < < CQ < < CQ CQ < < < 〇 CQ CQ o CQ 〇 o Q m D Q D 1 I < < < < < < < < < < < < < < < < < < < < < < CQ < < < CQ < < < U CQ U CQ CQ U u CQ Q QQ U 1 < < < < < < < < < < < < < < < < < < < < < < 0Q < < < CQ < < < U CQ u CQ CQ U u CQ CD U CQ L) 審 1 1 @ 1 § § § § § § § § § § § § § § § § § § 8 | 6¾ 8 1_15QQ_1 § § 8 § § S § § 1 1 I 1 雲 1 1 1 ! 馨 1 ! ! 穿 1 〇 1 | 1 I r^i 1 ,r | 雲 ITJ I ! 卜 I 00 I 1 1 1 I ! 震 I 穿 I 1 1 1 S 1 ! | 1 σ> 1 ! 1 | 1 | 1 1 ! I 導 is 1 I 1 g* §G 1 I I Έ Ί. Έ Έ. Έ η § § 1 I I S I § § § § S s s § § I / 1 1 £ I $ I 1 1 1 $ I I I 1 I <Ν 1 1 £ 叶 1 «r> 1 \〇 I 1 00 1 I ! I I 1 1 1 1 1 I 8 1 1 1 | 1 1 I 1 1 $ | St I i ΛΧ 1 1 1 1 0 1 Λί 1 <N I 1374198 第96114036號專利申請案說明書修正頁 修正曰期:100.8.23 如第2表所示,本發明之經複合被膜處理之含鋅鍍敷鋼材確實 在耐蝕性(平板試驗片與橫切加工試驗片的評價)、耐變黑性、塗裝 密著性、耐鹼性中任一者皆具有良好的性能。特別是,以複合被膜 之總被膜質量為100〜1500mg/m2之試驗片,顯示了在财姓性、而十變 黑性、塗裝密著性、耐鹼性之全部評價優異之結果。對此,比較例 之鍍敷鋼材中並非是可滿足耐蝕性、耐變黑性、塗裝密著性、耐鹼 性之全部性能者。 I:圖式簡單說明3
益 *»»、
20 S
Claims (1)
1374198 正日期:100.8.23 第96114036號專利申請案申請專利範圍g 十、申請專利範圍: 丨· 一種具有優異之耐蝕性、耐變黑性、塗裝密著性及耐鹼性之 經複合被膜處理之含鋅鍍敷鋼材,其特徵在於具有—將含有 鹼性鍅化合物、含釩(V〇2+)化合物、磷酸化合物、鈷化合 5 物、有機酸及水之PH7〜14的處理液塗布於鍍敷鋼材之表面上 後乾燥形成之複合被膜,且該複合被膜相對於1〇〇質量%之乙 元素,在比例上含有1〇〜45質量%之乂、5〜1〇〇質量%之卩、 0.1〜20質量%之(:〇、1〇〜9〇質量%之有機酸。 馨2.如申B月專利範圍第j項之具有優異之对餘性、耐變黑性、塗事 1〇 密著性及耐鹼性之經複合被膜處理之含鋅鍍敷鋼材,其中前 .. 述複合被膜之總被膜質量為50〜2000mg/m2。 3_如申吻專利範圍第2項之具有優異之对钱性、耐變黑性、塗穿 - 密著性及耐鹼性之經複合被膜處理之含鋅鍍敷鋼材,其中上 述複合被膜之總被膜質量為1〇〇〜15〇〇mg/m2。 Μ 4.如申請專利範圍第卜3項中任一項之具有優異之耐錄、耐變 黑性、塗裳密著性及耐驗性之經複合被膜處理之含鋅鐘數鋼 材,其中前述鍍敷鋼材之鍍敷層係由Zn及不可避免之不純物 之組成形成。 5.如申請專利範圍第卜3項中任—項之具有優異之耐絲、耐變 20 黑性、塗裝密著性及耐鹼性之經複合被膜處理之含鋅鍍數鋼 ; 材,其中前述鍍敷鋼材之鍍敷層除了含有鋅及不可避免之不 純物之外’還含有60質量%以下之μ、1〇質量%以下之Mg、之 質量%以下Si中1種以上之組成。 21
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