TW201638388A - 燃料槽用表面處理鋼板 - Google Patents

燃料槽用表面處理鋼板 Download PDF

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TW201638388A
TW201638388A TW105101892A TW105101892A TW201638388A TW 201638388 A TW201638388 A TW 201638388A TW 105101892 A TW105101892 A TW 105101892A TW 105101892 A TW105101892 A TW 105101892A TW 201638388 A TW201638388 A TW 201638388A
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Taiwan
Prior art keywords
fuel tank
steel sheet
chemical conversion
chromate
layer
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TW105101892A
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English (en)
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TWI597387B (zh
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Kiyokazu Ishizuka
Noriyuki Maekawa
Hiroaki Uramoto
Hidetoshi Shindo
Ikuo Kikuchi
Kenichiro Matsumura
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Nippon Steel & Sumitomo Metal Corp
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Publication of TW201638388A publication Critical patent/TW201638388A/zh
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/04—Tubes; Rings; Hollow bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/84—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for corrosive chemicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
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    • 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
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • 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
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    • 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
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    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
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    • 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
    • C23C22/42—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 phosphates
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    • 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
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    • 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
    • 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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    • 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
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    • C25D3/00—Electroplating: Baths therefor
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    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
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    • B60—VEHICLES IN GENERAL
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    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
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    • B60K2015/03032—Manufacturing of fuel tanks
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    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
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  • Chemical & Material Sciences (AREA)
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Abstract

一種燃料槽用表面處理鋼板，具備：鍍Zn層或鍍Zn-Ni合金層，係形成在鋼板之至少成為燃料槽內面之面；及無鉻酸鹽化學轉化皮膜層，其含有撥水撥油劑且位於成為前述燃料槽內面之面的前述鍍Zn層或前述鍍Zn-Ni合金層的上層；前述無鉻酸鹽化學轉化皮膜層在表面的水接觸角為70度以上，在表面的正十六烷接觸角為30度以上且70度以下。

Description

燃料槽用表面處理鋼板 發明領域
本發明係有關於一種燃料槽用表面處理鋼板。
發明背景
從對於最近環境規則之傾向而言，對不使用有害金屬的材料之市場需求提高。例如在汽車領域，從燃料槽的主流材料之鉛-錫合金鍍敷鋼板，轉換成為無鉛素材係進展中。在此，對於被要求在封入有燃料的環境下的內面耐蝕性(以下，稱為燃料耐蝕性)之燃料槽獨特的要求性能，係有揭示許多具有實績的鋅系鍍敷鋼板作為汽車的內外板(例如，參照以下的專利文獻1~3等)。
先前技術文獻 專利文獻
專利文獻1：日本特開平5-106058號公報
專利文獻2：日本特開平9-324279號公報
專利文獻3：日本特開2004-169122號公報
專利文獻4：日本特開2007-186745號公報
專利文獻5：WO2010/061964
專利文獻6：WO2008/059890
發明概要
但是，因為上述專利文獻1~3的技術，係將鉻酸鹽處理設設作前提者，與要求不使用有害金屬的材料之近年來的市場需求不相容。因此，有提案揭示無鉻酸鹽的燃料槽用鋅系鍍敷鋼板(例如，參照上述專利文獻4~6等)。相較於先前施行鉻酸鹽處理之鋅系鍍敷鋼板，此種無鉻酸鹽的鋅系鍍敷鋼板係在較嚴格的環境下之燃料耐蝕性(例如，較長期間的耐蝕性、及因加工引起產生皮膜損傷時之耐蝕性等)為不充分且有改良的必要。
在上述專利文獻4，係揭示一種有機樹脂主體的無鉻酸鹽皮膜。但是，此種有機樹脂主體的無鉻酸鹽皮膜，在燃料環境中長期間暴露時，有機樹脂因燃料而膨潤致使鍍敷界面的密著性低落。推斷此種有機樹脂的膨潤，係耐蝕性不足之主要原因。
在上述專利文獻5，係記載一種鋅鍍敷鋼板，其具有在鋅系鍍敷鋼板塗佈含有有機矽化合物及有機氟化合物之水性處理劑且乾燥或烘烤而形成之皮膜。又，在上述專利文獻6，係記載一種鋅鍍敷鋼板，其具有含有有機矽化合物、氟化合物、釩化合物及潤滑劑之複合皮膜。但是，雖然該等鋼板之耐蝕性提升，然而未賦予對劣化汽油之耐蝕性。
因此，本發明之目的係提供一種燃料槽用表面處 理鋼板，其在封入有含有如劣化汽油的有機酸之燃料、以及除了有機酸以外亦含有結露水之燃料等各種燃料的環境下，顯示優異的耐蝕性，而且具有良好的壓製加工性。又，本發明之目的係不使用鉛及鉻酸鹽處理而能夠得到上述的特性。
本發明者等係研討改善在無鉻酸鹽鋅系鍍敷鋼板的燃料耐蝕性之結果，得到以下的見解：使鋅系鍍敷層成為鍍Zn或鍍Zn-Ni合金之後，藉由對鍍敷層表面不僅是賦予撥水性而且亦賦予撥油性，而能夠顯著地改善燃料耐蝕性。又，本發明者等係得到以下的見解：過度地賦予撥油性時，相反地燃料耐蝕性低落，而且壓製加工性亦顯著地低落。基於該等見解而進行研討之結果，本發明者等係得到以下的見解：藉由在成為燃料槽內面之面，形成具有預定撥水性、及撥油性之皮膜，能夠得到具有優異的燃料耐蝕性及壓製加工性之鋼板。亦即就本發明的要旨而言係如以下。
(1)一種燃料槽用表面處理鋼板，該燃料槽用的表面處理鋼板具備：鍍Zn層或鍍Zn-Ni合金層，係位於成為基鐵的燃料槽內面之面、或成為燃料槽內面之面及成為燃料槽外面之面；及無鉻酸鹽化學轉化皮膜層，其含有撥水撥油劑且位於前述鍍Zn層或前述鍍Zn-Ni合金層的上層；前述無鉻酸鹽化學轉化皮膜層在表面的水接觸角為70度以上，在表面的正十六烷接觸角為30度以上且70度以 下。
(2)如(1)所述之燃料槽用表面處理鋼板，其僅在前述冷軋鋼板之成為燃料槽內面之面具備前述鍍Zn層或前述鍍Zn-Ni合金層及前述無鉻酸鹽化學轉化皮膜層，且在前述冷軋鋼板之成為燃料槽外面之面不具有前述鍍Zn層或前述鍍Zn-Ni合金層及前述無鉻酸鹽化學轉化皮膜層。
(3)如(2)所述之燃料槽用表面處理鋼板，其中前述冷軋鋼板單面之Zn及/或Ni的附著量為0.01~0.5g/m2。
(4)如(1)至(3)項中任一項所述之燃料槽用表面處理鋼板，其中前述鍍Zn層或前述鍍Zn-Ni合金層的附著量係每一面為5~40g/m2。
(5)如(1)至(4)項中任一項所述之燃料槽用表面處理鋼板，其中相對於前述鍍Zn-Ni合金層的總質量，前述鍍Zn-Ni合金層的Ni含有率為9~14質量%。
(6)如(1)至(5)項中任一項所述之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層的附著量為0.1~2g/m2。
(7)如(1)至(6)項中任一項所述之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層含有氟系撥水撥油劑作為前述撥水撥油劑。
(8)如(1)至(7)項中任一項所述之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層更含有聚烯烴系潤滑劑。
(9)如(1)至(7)項中任一項所述之燃料槽用表面處理鋼 板，其中前述無鉻酸鹽化學轉化皮膜層係無機系皮膜，且不含前述撥水撥油劑以外的有機樹脂成分。
(10)如(8)所述之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層係無機系皮膜，且不含前述撥水撥油劑及前述聚烯烴系潤滑劑以外的有機樹脂成分。
依照本發明，能夠提供一種燃料槽用表面處理鋼板，其在封入有含有如劣化汽油的有機酸之燃料、以及除了有機酸以外亦進一步含有結露水之燃料等各種燃料的環境下，顯示優異的耐蝕性，而且具有良好的壓製加工性。
用以實施發明之形態
本發明係有關於一種鋅系燃料槽用鋼板，其對各種燃料具有優異的耐蝕性及壓製加工性，而且不施行鉛及鉻酸鹽處理而對環境友善。又，本發明係有關於一種使用在以汽車、兩輪車、產業機械、建築機械為首、以及封入有燃料之燃料槽或該燃料槽的零件之鋼板。
本發明之燃料槽用鋼板具有：鍍Zn層或鍍Zn-Ni合金層(以下，亦稱為鍍敷層)，係位於成為基鐵的燃料槽內面之面(單面)、或成為燃料槽內面之面及成為燃料槽外面之面(雙面)；無鉻酸鹽化學轉化皮膜層(以下，亦稱為化學轉化皮膜層)，其含有撥水撥油劑且在前述鍍Zn層或前述鍍 Zn-Ni合金層的上層。又，前述化學轉化皮膜層表面的水接觸角為70度以上，化學轉化皮膜層表面的正十六烷接觸角為30度以上且70度以下。
本發明的鋼板，係成為燃料槽外面之面(以下，稱為外面)，可具有鍍Zn層或鍍Zn-Ni合金層，亦可不具有鍍Zn層或鍍Zn-Ni合金層。但是，為了使鋼板的熔接性成為良好，成為燃料槽外面之面係以不具有鍍敷層為佳。又，例如鋼板係使用在如兩輪車用燃料槽之重視燃料槽外面塗裝的美觀之用途時，為了使塗裝外觀成為良好，燃料槽外面以不具有鍍敷層為佳。另一方面，鋼板係使用在燃料槽外面亦被要求高度的耐蝕性之用途時，燃料槽外面係以具有鍍敷層為佳。本發明的鋼板，係能夠按照用途而控制有無外面及內面的鍍敷層。又，在成為上述燃料槽外面之面的鍍Zn層或鍍Zn-Ni合金層的上層，或是在不具有鍍Zn層或鍍Zn-Ni合金層之鋼板面的上層，係不形成無鉻酸鹽化學轉化皮膜層。上述水接觸角及正十六烷接觸角能夠藉由使用接觸角計之眾所周知的測定方法來測定。
成為燃料槽內面之面的無鉻酸鹽化學轉化皮膜層表面的水接觸角為70度以上，正十六烷接觸角為30度以上且70度以下係必要的。水接觸角小於70度時，劣化汽油耐蝕性不足。較佳為80度以上。水接觸角的上限沒有特別規定(原理上係不會大於180度)，但通常鍍Zn層或鍍Zn-Ni合金層上的無鉻酸鹽化學轉化皮膜層可達成的水準之上限在120度左右。而推斷水接觸角較大時，避免來自劣化汽油 中的有機物等腐蝕因素濃化而成之結露水的影響之遮斷效果較大且耐蝕性提升。為了得到充分的劣化汽油耐蝕性，只有如上述地規定水接觸角係不夠的，還必須進一步控制油接觸角。
又，在本發明，成為燃料槽內面之面的無鉻酸鹽化學轉化皮膜層表面的正十六烷接觸角為30度以上且70度以下。又，無鉻酸鹽化學轉化皮膜層表面的正十六烷接觸角係較佳為55度以上且70度以下。在此，正十六烷係使用作為燃料油的模擬的成分。化學轉化皮膜層表面的正十六烷接觸角小於30度時，對劣化汽油之耐蝕性為不足。該理由雖未明確，但認為接觸角較小時，係由於劣化汽油以在壓製加工等所產生的傷痕部位作為起點而侵蝕皮膜。又，化學轉化皮膜層表面的正十六烷接觸角大於70度時，在鋼板的相反面(成為燃料槽外面之面)的一次防鏽性係顯著地低落。其理由，係因為通常燃料槽用鋼板在製造生產線形成鍍敷層、及化學轉化皮膜層形成之後，塗佈一次防鏽用防鏽油且被捲取成為鋼捲狀出貨。具體而言，鋼板被捲取成為鋼捲狀時，成為燃料槽外面之面(亦即，無化學轉化皮膜層之鍍Zn面或鍍Zn-Ni合金面、或是非鍍敷面)會與成為燃料槽內面之面(亦即，具有撥水、及撥油性之無鉻酸鹽化學轉化皮膜層表面)相對面。在此，成為燃料槽內面之面的正十六烷接觸角大於70度時，化學轉化皮膜層表面係將防鏽油過度地收縮且為鋼捲狀的堆疊狀態時，此種影響亦會對與成為燃料槽內面之面相對面之燃料槽外面產生波及， 故於高溫高濕條件下時，會在與成為燃料槽內面之面相對面之面(亦即，成為燃料槽外面之面)發生從防鏽油不足的部位開始生鏽之情形。特別是成為燃料槽外面之面為非鍍敷面時，該現象係致命性的。
又，上述一次防鏽較差的鋼板，係在鋼捲狀態下被長期保管之後，在製造燃料槽時，塗裝性亦變差。通常，在使用鋼板所製成的燃料槽，內面係經面處理後的鋼板之狀態，而外面係被塗裝。特別是在兩輪車用槽，因為重視燃料槽外面的塗裝之美觀，所以成為外面之面的塗裝性係重要的特性。在此，即便在一次防鏽試驗不產生能夠目視確認的生鏽等異常，稍微的表層氧化膜斑點亦有引起塗裝斑點之情形。因此，藉由將成為內面之面的正十六烷接觸角設為70度以下，能夠進一步抑制防鏽性及塗裝性低落。而且成為外面之面，係以設為非鍍敷面為較佳。這是因為在成為外面之面設置有鍍Zn層或鍍Zn-Ni合金層時，即便成為內面之面的正十六烷接觸角為本發明範圍之30度以上且在一次防鏽試驗不生鏽，亦容易產生稍微的鋅氧化膜斑點且有塗裝性低落之可能性。
又，正十六烷接觸角大於70度時，因為對劣化汽油之耐蝕性有低落之可能性，乃是不佳。這是因為如後述，正十六烷接觸角大於70度時，油收縮變為顯著且壓製加工性低落，而且有皮膜和鍍敷層損傷變大之可能性。
另一方面，在本發明之鋼板，因為成為燃料槽內面之面的正十六烷接觸角為30度以上且70度以下，所以雖 然壓製加工時會使油某種程度收縮，但是在壓製加工係實用上不成為問題。又，在本發明，成為燃料槽外面之面為鍍Zn、或鍍Zn-Ni合金、或是非鍍敷面時，因為該等面不會使油收縮而可使得壓製加工性進一步提升。如此，本發明之鋼板藉由將成為燃料槽內面之面、及成為燃料槽外面之面設為不同的規格，可進一步改善壓製加工性。
在此，在本發明之鋼板，被使用作為母材之鋼板(基鐵)係沒有特別限定，只要通常能夠使用作為鋅系鍍敷鋼板的母材之鋼板，任何鋼板均能夠使用。
在本發明之鋼板(基鐵)的至少一面所形成之鍍Zn層或鍍Zn-Ni合金層，係至少含有鋅、或由鋅及鎳所構成的合金之合金鍍敷層。此種鍍Zn層或鍍Zn-Ni合金層可藉由例如電鍍法等眾所周知的鍍敷法來形成。
在本發明之鋼板的鍍Zn層或鍍Zn-Ni合金層的每一面之附著量，係以5~40g/m2為佳。鍍Zn層或鍍Zn-Ni合金層的每一面之附著量小於5g/m2時，因為對劣化汽油之耐蝕性容易不足，乃是不佳。又，鍍Zn層或鍍Zn-Ni合金層的每一面之附著量大於40g/m2時，因為成本上不利，乃是不佳。
又，相對於鍍Zn-Ni合金層的總質量，在鍍Zn-Ni合金層之Ni含有率係以9~14質量%為佳。Ni含有率為該範圍時，特別是對劣化汽油之耐蝕性變為良好。又，鍍Zn層或鍍Zn-Ni合金層亦可含有眾所周知的第三成分(例如，Fe、Co、Sn、Cr等的金屬)，亦可對鍍Zn層或鍍Zn-Ni合金層的下層施行眾所周知的預鍍敷(例如，Fe、Ni等的預鍍敷)。
而且，本發明之燃料槽用鋼板，係在成為燃料槽內面之面的鍍Zn層或鍍Zn-Ni合金層的上層具有含有撥水撥油劑之無鉻酸鹽化學轉化皮膜層(以下，亦稱為化學轉化皮膜層)。在本發明之鋼板之無鉻酸鹽化學轉化皮膜層的附著量，係以0.1~2g/m2為佳。無鉻酸鹽化學轉化皮膜層的附著量小於0.1g/m2時，因為對劣化汽油之耐蝕性不足，乃是不佳；無鉻酸鹽化學轉化皮膜層的附著量大於2g/m2時，因為加工性、熔接性有低落之情形，乃是不佳。
在本發明之鋼板，為了實現成為燃料槽內面之面的水接觸角、及正十六烷接觸角，必須使無鉻酸鹽化學轉化皮膜層含有撥水撥油劑。特別是使無鉻酸鹽化學轉化皮膜層含有氟系撥水撥油劑為佳。作為氟系撥水撥油劑，係只要具有C-F鍵之氟系樹脂，能夠使用任何物，例如能夠使用聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷基乙烯醚共聚物、聚氯三氟乙烯、聚偏二氟乙烯(polyvinylidene fluoride)、聚氟乙烯、乙烯-四氟乙烯共聚物、乙烯-氯三氟乙烯共聚物、全氟烷基含有聚合物等。相對於化學轉化皮膜層整體的固體成分質量，作為在無鉻酸鹽化學轉化皮膜層之氟系撥水撥油劑的含量，係以0.1質量%以上且10質量%以下為佳，以1質量%以上且5質量%以下為較佳。
又，本發明之鋼板的無鉻酸鹽化學轉化皮膜層，亦可進一步含有聚烯烴系潤滑劑。此時，能夠減低在將鋼板進行壓製加工時之滑動性。相對於化學轉化皮膜層整體 的固體成分質量，作為在無鉻酸鹽化學轉化皮膜層之聚烯烴系的潤滑劑含量，係以0.1質量%以上且10質量%以下為佳，以1質量%以上且5質量%以下為較佳。
本發明之鋼板的無鉻酸鹽化學轉化皮膜層，可為有機系皮膜層，亦可為無機系皮膜層。但是，要求對劣化汽油更高度的耐蝕性時，無鉻酸鹽化學轉化皮膜層係不含有有機樹脂成分、或是含有最少化的有機樹脂成分為佳。推斷這是因為在無鉻酸鹽化學轉化皮膜層所含有的有機樹脂成分，受到燃料引起的膨潤作用而使耐蝕性低落之緣故。又，作為在無鉻酸鹽化學轉化皮膜層所含有的有機樹脂成分，具體而言，可舉出丙烯酸樹脂、烯烴樹脂、胺甲酸酯樹脂、環氧樹脂、聚酯樹脂等。相對於化學轉化皮膜層整體的固體成分質量，在無鉻酸鹽化學轉化皮膜層之該等有機樹脂成分的含量，係以50質量%以下為佳，較佳為30質量%以下，最佳為0質量%。
又，本發明之鋼板的無鉻酸鹽化學轉化皮膜層，亦可含有矽烷偶合劑、矽烷偶合劑的聚縮合物、氧化矽、矽酸鹽、磷酸、磷酸鹽等作為無機系成分。本發明之鋼板的無鉻酸鹽化學轉化皮膜層係可以將該等單獨或是複合、或與上述的有機樹脂成分混合而形成。又，亦可在無鉻酸鹽化學轉化皮膜層，在不使特性變差的範圍，調配以上述的聚烯烴系潤滑劑為首、以及其它成分。
而且，本發明之鋼板的無鉻酸鹽化學轉化皮膜係能夠使用眾所周知的方法來形成。例如能夠藉由調製含有 上述說明的預定成分之塗佈液，將所調製的塗佈液使用桿塗佈器、輥塗佈機等的眾所周知的方法塗佈在鍍Zn層或鍍Zn-Ni合金層的上層之後，使塗佈膜在預定加熱溫度加熱及乾燥來形成。
如上述，為了使鋼板的熔接性成為良好，或是為了使燃料槽外面的塗裝外觀成為良好，在成為燃料槽外面之面，係以不具有鍍敷層為佳。為了使外面成為不具有鍍敷層的狀態，能夠採用在進行電鍍時，不對非鍍敷面側進行通電之方法。或是在進行鍍敷之後，將非鍍敷面側藉由電化學(例如陽極電解處理)或機械(例如毛刷磨削)方法除去鍍敷層之方法。又，亦能夠組合前述的方法。
使用前述記載的方法，本發明的鋼板之非鍍敷面(燃料槽外面)，係能夠成為Zn及/或Ni完全不附著。此時，Zn及/或Ni的附著量為0。如上述，其係為了使鋼板的熔接性及塗裝性提升。而附著量為0.01~0.5g/m2，以0.01~0.3g/m2為佳，較佳是以0.01~0.1g/m2為佳。
使用該等方法所形成的非鍍敷面(外面)之接觸角，係正十六烷接觸角為小於10度，較佳是小於5度為佳。藉此，能夠改善壓製加工性和塗裝性。為了確實地成為前述接觸角，抑制鋼板的表面氧化係有效的，就此點而言，係以在非鍍敷面側亦存在極微量的Zn及或Ni為佳。其附著量係以0.01~0.5g/m2為佳。
實施例
其次，舉出實施例及比較例而更具體地說明本發 明。
首先，將表1所顯示之各種非鍍敷鋼板，將單面鍍敷鋼板或雙面鍍敷鋼板使用作為原板而製成燃料槽用表面處理鋼板。又，表1所顯示的鋼板均是板厚0.8mm的深引伸用添加Ti的極低碳鋼板，且在原板的只有單面(成為燃料槽內面之面)或雙面形成各種化學轉化皮膜層。又，將構成各種化學轉化皮膜層之基體皮膜的調配顯示在表2。又，在表2所顯示的基體皮膜，以各自表5所顯示的比率添加表3所顯示的聚烯烴系潤滑劑、及表4所顯示的氟系撥水撥油劑且形成各種化學轉化皮膜層。
又，在表2，「胺甲酸酯樹脂(*1)」係表示酯系胺甲酸酯樹脂，「離子聚合物樹脂(*2)」係表示Na中和離子聚合物樹脂，「矽烷偶合劑(*3)」係表示3-環氧丙氧基丙基三甲氧基矽烷，「矽烷偶合劑寡聚物(*4)」係表示3-環氧丙氧基丙基三甲氧基矽烷與3-胺丙基三乙氧基矽烷之1：1聚縮合物(分子量約3000)，「膦酸(*5)」係表示1-羥基亞乙基-1,1’-二膦酸。又，在表2，「-」係表示不調配對應之成分。
[表5]
又，在表5，「-」係表示不調配對應之成分。
接著，揭示表6~表8之試樣製造條件、及所製成的鋼板之性能評價結果。在此，成為燃料槽內面之面的接觸角係如以下測定。
(水接觸角)
使用接觸角計(協和界面科學製DM901)在25℃的環境下滴下離子交換水3μl(微升)且測定60秒後的靜態接觸角。
(正十六烷接觸角)
使用接觸角計(協和界面科學製DM901)在25℃的環境下滴下正十六烷3μl(微升)且測定60秒後的靜態接觸角。
性能評價係如以下進行。
(一次防鏽性)
在所製成的試樣，將防鏽油(Parker興產Noxrust530)進行極薄塗油(約0.1g/m2)之後，模擬鋼捲狀態而以成為內面之面與成為外面之面接觸的方式進行重疊捆包。在50℃98%RH環境下保管1個月之後，打開捆包而觀察成為燃料槽外面之面的生鏽狀況。又，觀察結果係基於以下的基準進行評價。
○：未產生鏽、變色
△：產生白鏽或變色
×：產生紅鏽
(塗裝性)
進行評價成為外面之面的塗裝性。通常，因為汽車或兩輪車用燃料槽外面，係施行塗裝前處理用化學轉化處理之後，進行塗裝，所以塗裝外觀係被塗裝前處理用化學轉化處理後的外觀支配。因此，在施行塗裝前處理用化學轉化處理施行後的鋼板，係進行評價成為外面之面的外觀。又，塗裝前處理用化學轉化處理係如以下進行。
使用由六氟鋯酸、硝酸Al、及聚乙烯亞胺所構成之P-free(無磷)化學轉化處理(特許第5274560的實施例1)來形成化學轉化皮膜層。隨後，對化學轉化皮膜層形成後的 鋼板進行目視判定(但是目視難以辨別時，係進行掃描型電子顯微鏡(SEM：Scanning Electron Microscope)觀察))，基於以下的基準進行評價。
◎：均勻的外觀
○：容許水準的輕微斑點
△：顯著斑點
×：產生鏽垢(無化學轉化皮膜層)
(保管後塗裝性)
與前述一次防鏽性評價同樣地使用保管1個月後的試樣，進行與前述塗裝性評價相同的塗裝前處理用化學轉化處理，且以相同基準進行評價。
(加工性(滑動性))
藉由引伸珠試驗(drawbead test)進行評價。使用凸珠粒前端5R、凹肩3R的模具，將切斷成為30mm寬度之試樣(將防鏽油(Parker興產Noxrust530)進行塗油)在壓黏荷重500kg~1200kg的範圍以200mm/min的速度進行拉拔100mm。隨後，從壓黏荷重與拉拔荷重之關係求取摩擦係數。又，在凸珠粒側，係安裝成為燃料槽內面之面。又，在珠粒模具係不進行塗油且在每1次試驗將模具的油擦去而進行試驗。摩擦係數係基於下述的基準而進行評價。
◎：摩擦係數0.13以下
○：0.13<摩擦係數≦0.15以下
△：0.15<摩擦係數<0.2
×：摩擦係數0.2以上
(劣化汽油耐蝕性)
將鋼板成形成為模擬燃料槽而成之內徑50mm、深度35mm的圓筒狀，使用脫脂處理將油除去之後，在內面底使用切刀產生達到基鐵為止之傷痕(模擬在壓製加工的傷痕)。隨後，將模擬劣化汽油之試驗液(含有甲酸100ppm、乙酸300ppm、氯化物離子100ppm、水1.0體積%之汽油)，封入成形後的鋼板且在40℃保持2個月。隨後，基於下述的基準進行評價鋼板的腐蝕狀況。
◎：無腐蝕
○：輕微生鏽(無因腐蝕引起板厚減少之水準)
△：部分產生腐蝕
×：遍及全面產生腐蝕
如表6~表8所顯示的結果，得知本發明之實施例係任一評價項目均顯示○以上的評價，而具有良好的特性。具體而言，關於一次防鏽性，在正十六烷接觸角大於本發明的上限之比較例5、6、13、14，係能夠觀察到生鏽。又，關於塗裝性，係除了在成為外面之面形成有化學轉化皮膜層之比較例17~22以外，任一實施例及比較例均顯示◎之良好的評價；關於保管後塗裝性，在一次防鏽生鏽之比較例5、6、13、14，評價結果為顯著地變差。而且，如表9所顯示，關於保管後塗裝性，在成為外面之面亦設置有鍍Zn-Ni合金層之實施例20~38，係產生容許水準的斑點，得知本發明之鋼板係以將外面設為非鍍敷面為較佳。又，比較例9~12、15、16，雖然在成為外面之面有鍍Zn-Ni合金層，但是因為在成為內面之面之正十六烷接觸角小於本發明的下限，所以保管後塗裝性為良好。但是，因為在成為內面之面之正十六烷接觸角小於本發明的下限，所以耐蝕性低落。關於加工性(滑動性)，正十六烷接觸角大於本發明的上限之比較例5、6、13、14、及即便正十六烷接觸角為本發明的範圍內而在內外面雙面形成有化學轉化皮膜層之比較例18、19、21、22，係加工性顯著地低落。又，比較本發明的實施例之間時，添加有聚烯烴蠟之實施例1、8、13、14、20、27、32、33，評價為較佳。關於對劣化汽油之耐蝕性，得知本發明的實施例係任一者均良好，特別是使用不含有聚烯烴蠟和氟系樹脂以外的有機樹脂成分之無機系皮膜作為無鉻酸鹽化學轉化皮膜層之實施例3~16、22~35、43~66為較優 異。又，得知正十六烷接觸角為55度以上之實施例4~16、23~35、43~66為較優異。又，參照實施例55~60時，得知化學轉化皮膜層的附著量為0.3g/m2以上時，耐蝕性為較優異。而且，參照實施例39~42時，得知鍍Zn-Ni合金層的每一面之附著量為15g/m2以上時，耐蝕性為較優異。
針對表1所顯示之原板的單面鍍敷材，詳細地分析其非鍍敷面側時，任一者均能夠檢測出Zn、Ni為0.1g/m2左右。在表9所顯示的結果，係為了確認非鍍敷面側的微量Zn、Ni之影響，使用表1的原板之S/20及S/EG40，鍍敷面側係進行膠帶密封之後，使用#800的研磨紙將非鍍敷面側進行研磨之後，進行陽極電解處理而將微量的Zn、Ni完全除去(*1：實施例69、71)。或是使用S/20及S/EG40，鍍敷面側係進行膠帶密封之後，對非鍍敷面側進行預定量Zn或Ni的電鍍(*2：實施例70、72、74~77)。隨後，與前面的例子同樣地進行預定皮膜處理，來調製實施例69~77的試樣。將該等試樣、及在表6~表8所試樣之中選定實施例5、實施例24、實施例58、實施例59、比較例22而進行外面的接觸角測定、塗裝性評價、保管後塗裝性評價。該等評價方法、基準係 與前面所揭示者相同。
又，針對該等試樣進行評價接縫熔接性。以成為內面之面之間係成為內側的方式合在一起。接縫熔接條件係如以下。
．電極：Cu-Cr合金且具有中央部為15mmR的4.5mm寬度、端部為4mmR的寬度8mm的剖面之圓盤狀電極
．熔接方法：雙層重疊、搭接縫熔接(lap seam welding)
．加壓力：400kgf(又，1kgf係約9.8N)
．通電時間：2/50秒通電on、1/50秒通電off
．冷卻：內部水冷、及外部水冷
．熔接速度：2.5m/分鐘
使熔接電流變化而求取得到適當的熔核(nugget)之電流的範圍。
將結果顯示在表10。在搭接縫熔接，認為適當的電流範圍為3kA左右以上時，實用上係沒有問題，以較廣闊者為佳。因而，比較實施例5、24時，得知相較於雙面鍍敷，係以單面鍍敷為佳。又，比較實施例5、58、59時，得知化學轉化皮膜層的被膜量，係以將1.2g/m2左右設為上限為佳。
以上，詳細地說明了本發明的適合實施形態，但是本發明係不被如此的例子限定。只要具有屬於本發明技術的領域之通常的知識者，係清楚明白在申請專利範圍所記載的技術思想範疇內，能夠創造出各種的變更例或修正例，應了解該等當然係屬於本發明的技術範圍。
產業上之利用可能性
因為本發明係提供一種燃料槽用表面處理鋼板，其在封入有含有如劣化汽油的有機酸之燃料、以及除了有機酸以外亦進一步含有結露水之燃料等各種燃料的環境下，亦顯示優異的耐蝕性，而且具有良好的壓製加工性，所以在產業上係有用的。
而且，本發明係提供一種使成為燃料槽外面之面成為裸金屬(bare metal)，使成為燃料槽內面之面成為無鉻酸鹽化學轉化皮膜，而使內外面成為不同狀態的表面之鋼板。此種本發明的鋼板係具備從燃料槽的製造開始至使用為止所必要的所有性能，包括：(i)將鋼板且熔接而成為槽形狀時所必要的加工性優異；(ii)將加工後的燃料槽進行塗裝且必須提高外觀的美觀時具有優異的塗裝性；以及(iii)製造後長年使用燃料槽時所必要的耐蝕性優異。就內外面不同狀態的表面互相作用而能夠進一步發揮內外面的性能差異而言，本發明的鋼板係具有先前所沒有的效果。

Claims (10)

  1. 一種燃料槽用表面處理鋼板，具備：鍍Zn層或鍍Zn-Ni合金層，係位於成為基鐵的燃料槽內面之面、或成為燃料槽內面之面及成為燃料槽外面之面；及無鉻酸鹽化學轉化皮膜層，其含有撥水撥油劑且位於前述鍍Zn層或前述鍍Zn-Ni合金層的上層；其中前述無鉻酸鹽化學轉化皮膜層在表面的水接觸角為70度以上，在表面的正十六烷接觸角為30度以上且70度以下。
  2. 如請求項1之燃料槽用表面處理鋼板，其僅在前述冷軋鋼板之成為燃料槽內面之面具備前述鍍Zn層或前述鍍Zn-Ni合金層及前述無鉻酸鹽化學轉化皮膜層，且在前述冷軋鋼板之成為燃料槽外面之面不具有前述鍍Zn層或前述鍍Zn-Ni合金層及前述無鉻酸鹽化學轉化皮膜層。
  3. 如請求項2之燃料槽用表面處理鋼板，其中前述冷軋鋼板之成為燃料槽外面之面的Zn及/或Ni的附著量為0.01~0.5g/m2。
  4. 如請求項1至3項中任一項之燃料槽用表面處理鋼板，其中前述鍍Zn層或前述鍍Zn-Ni合金層的附著量係每一面為5~40g/m2。
  5. 如請求項1至4項中任一項之燃料槽用表面處理鋼板，其 中相對於前述鍍Zn-Ni合金層的總質量，前述鍍Zn-Ni合金層的Ni含有率為9~14質量%。
  6. 如請求項1至5項中任一項之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層的附著量為0.1~2g/m2。
  7. 如請求項1至6項中任一項之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層含有氟系撥水撥油劑作為前述撥水撥油劑。
  8. 如請求項1至7項中任一項之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層更含有聚烯烴系潤滑劑。
  9. 如請求項1至7項中任一項之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層係無機系皮膜，且不含前述撥水撥油劑以外的有機樹脂成分。
  10. 如請求項8之燃料槽用表面處理鋼板，其中前述無鉻酸鹽化學轉化皮膜層係無機系皮膜，且不含前述撥水撥油劑及前述聚烯烴系潤滑劑以外的有機樹脂成分。
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