TWI434962B - A steel plate for container having excellent corrosion resistance - Google Patents

A steel plate for container having excellent corrosion resistance Download PDF

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Publication number
TWI434962B
TWI434962B TW100110346A TW100110346A TWI434962B TW I434962 B TWI434962 B TW I434962B TW 100110346 A TW100110346 A TW 100110346A TW 100110346 A TW100110346 A TW 100110346A TW I434962 B TWI434962 B TW I434962B
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Taiwan
Prior art keywords
steel sheet
amount
adhesion
plating layer
layer
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Application number
TW100110346A
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English (en)
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TW201142090A (en
Inventor
Shigeru Hirano
Makoto Kawabata
Original Assignee
Nippon Steel & Sumitomo Metal Corp
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Publication of TW201142090A publication Critical patent/TW201142090A/zh
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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
    • 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
    • C23C22/07—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
    • 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
    • C23C22/24—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 hexavalent chromium compounds
    • 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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
    • 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
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    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/361—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 fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/021—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 only coatings only including layers of metallic material including 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
    • 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
    • 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
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    • 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
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D11/02—Anodisation
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • 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
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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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    • 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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    • Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
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    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
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    • 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.]
    • Y10T428/273—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.] of coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)

Description

耐蝕性優異之容器用鋼板 技術領域
本發明係有關於一種容器用鋼板，特別係有關於一種使用於2片罐及3片罐，且耐蝕性、密著性、熔接性優異之容器用鋼板。
 背景技術
於飲料罐領域所使用之鐵製容器主要存在有2片罐與3片罐。
2片罐係指罐底與罐身部為一體之罐體，廣為周知的有DrD罐、DI罐等，藉沖壓加工、拉伸加工、彎曲回彎(bending/returning)加工、或組合該等加工而成形。於該等罐體所使用之鋼板，有鍍錫鋼皮(鍍Sn鋼板)或TFS(電解鉻酸處理鋼板(無錫鋼板))，依據用途或加工方法而分別使用。
3片罐係罐身部與底部不為一體之罐體，以熔接進行罐身部之製造的熔接罐為主流。罐身部之素材係使用附有輕基重之鍍Sn鋼板或鍍Ni鋼板。又，底部之素材係使用TFS等。
為了對消費者宣傳商品價值，均於2片罐或3片罐外面施行有印刷。又，為確保耐蝕性，於罐內面塗佈有樹脂。習知之2片罐係於進行罐體成形後，以噴霧等塗裝罐內面側，於罐外面側則施行有曲面印刷。又，最近，正盛行將預先積層有PET薄膜之鋼板成形為罐的積層2片罐(專利文獻1、專利文獻2)。又，構成3片罐之熔接罐，以往，係於罐內面施行塗裝且將於罐外面施行有印刷之鋼板熔接，製造罐體，但亦正盛行使用積層有預先印刷完成之PET薄膜的積層鋼板取代塗裝完工製程所製造的3片罐(專利文獻3、專利文獻4)。
於製造2片罐時，於容器用鋼板施行沖壓加工或拉伸加工、彎曲回彎加工，又，於製造3片罐時，亦對容器用鋼板施行頸縮加工或凸緣加工，視情況，為了設計性而施行延展加工。因此作為容器用鋼板使用之積層鋼板正追求可隨著該等加工之優異薄膜密著性。
鍍Sn鋼板藉由Sn之優異的犧牲性防作用對酸性之內容物仍具有優異之耐蝕性，但因其最表層存在有脆弱之Sn氧化物，故薄膜之密著性不穩定。因此，於接受前述加工時，有薄膜剝離、或薄膜與鋼板之密著力不充分處成為腐蝕產生起點等問題。
因此，有人使用加工性及密著性優異且可熔接之鍍Ni鋼板，作為容器用之積層鋼板(專利文獻5)。很久以前就揭示有鍍Ni鋼板(例如專利文獻9)。鍍Ni鋼板除了如鍍Sn鋼板般係表面無光澤者之外，藉由添加有光澤劑之鍍Ni方法施行有光澤電鍍者亦眾所周知(專利文獻6、專利文獻7)。
然而，眾所周知的是，因Ni未具有如Sn之犧牲性防蝕作用，對於酸性飲料等腐蝕性高之內容物，將產生由鍍Ni層之小孔等缺陷部朝板厚方向進行腐蝕的穿孔腐蝕，於短期間內形成開孔。因此，正在追求提升鍍Ni鋼板之耐蝕性。為了減輕穿孔腐蝕，亦發明有調整鋼成分，使所電鍍之鋼板的電位靠近貴重方向的鍍Ni鋼板(專利文獻8)。
先前技術文獻 專利文獻
[專利文獻1]日本專利特開2000-263696號公報
[專利文獻2]　日本專利特開2000-334886號公報
[專利文獻3]　日本專利3060073號公報
[專利文獻4]　日本專利2998043號公報
[專利文獻5]　日本專利特開2007-231394號公報
[專利文獻6]　日本專利特開2000-26992號公報
[專利文獻7]　日本專利特開2005-149735號公報
[專利文獻8]　日本專利特開昭60-145380號公報
[專利文獻9]　日本專利特開昭56-169788號公報
專利文獻8所記載之發明中，對於穿孔腐蝕的減輕可得到一定之效果，但正期望更加提升之耐蝕性。又，因專利文獻8中記載之發明限定為鋼成分，故僅適用一部分之用途。因此，正尋求可適用多樣之內容物或罐形狀的鍍Ni鋼板。
本發明係有鑑於前述情事而作成者，並以提供一種耐蝕性優異之容器用鋼板作為目的。
本發明人等致力研究之結果，發現藉使鍍Ni層含有特定範圍之Co，可抑制基質鐵之穿孔腐蝕，且發揮極為優異之效果以達成前述目的。
本發明之容器用鋼板係依據前述觀察所得知識者，較詳細而言，係一種耐蝕性、密著性、熔接性優異之容器用鋼板，其特徵在於具有以下而成者：鋼板；於前述鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co的鍍Ni層；及於前述鍍Ni層表面以Cr換算量計為1~40mg/m2 之附著量所形成的鉻酸鹽皮膜層。
依據本發明，更提供一種耐蝕性、密著性、熔接性優異之容器用鋼板，其特徵在於具有以下而成者：鋼板；於前述鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co的鍍Ni層；及於前述鍍Ni層表面以Zr量計為1~40mg/m2 之附著量所形成的含有Zr之皮膜層。
具有前述構造之本發明之容器用鋼板發揮優異之效果的理由，依據本發明人等之觀察所得知識，可如以下地推定。
換言之，本發明人等為了對應穿孔腐蝕之減輕，針對鍍Ni層中之微量添加元素對耐蝕性所造成之影響，進行了各種檢討時，發現藉於鍍Ni層含有特定量(微量)之Co，於由鍍Ni層之小孔等缺陷部進行腐蝕時，係沿著鍍Ni層與基質鐵之界面進行腐蝕的現象(參照第1圖)。
本發明人更加深入地研究，結果，亦更發現藉由具有沿著基質鐵與鍍Ni層之界面進行腐蝕的傾向，受到了朝向基質鐵之「厚度」方向的穿孔腐蝕抑制。
該現象依據本發明人等之觀察所得知識，推測係藉由以下之機制所進行者。換言之，於微量添加有Co之鍍Ni鋼板中，相對於Ni於電化學上較為卑之Co溶解於鍍Ni層中，而呈經溶解之Co離子析出於鍍Ni層與基質鐵之界面的基質鐵側的狀態。腐蝕主要係於經析出之Co與基質鐵之間產生，被視為於鍍Ni層與基質鐵之界面進行腐蝕。
又，依據本發明人等之觀察所得知識，可知經離子化之Co緩和鍍Ni層上之鉻酸鹽層或含有Zr之皮膜層之鈍化效果，而對應於基質鐵之孔蝕(Fe之氧化反應)的氧或氫之還原反應亦可於鍍Ni層上產生。
本發明人等利用該現象，而完成發明具有前述構造，且密著性、耐蝕性、熔接性優異之容器用鋼板。
本發明，例如，可具有以下之態樣。
[1]一種耐蝕性、密著性、熔接性優異之容器用鋼板，其特徵在於，具有：鋼板；於前述鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co的鍍Ni層；及於前述鍍Ni層表面以Cr換算量計為1~40mg/m2 之附著量所形成的鉻酸鹽皮膜層。
[2]如[1]記載之容器用鋼板，其中前述鍍Ni層之Ni量係0.35~2.8g/m2 。
[3]如[1]或[2]記載之容器用鋼板，其中前述鍍Ni層之Co含有率係0.3~92ppm。
[4]如[1]~[3]中任1項記載之容器用鋼板，其中前述鉻酸鹽皮膜層之Cr換算附著量係1.2~38mg/m2 。
[5]一種耐蝕性、密著性、熔接性優異之容器用鋼板，其特徵在於，具有：鋼板；於前述鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co的鍍Ni層；及於前述鍍Ni層表面以Zr量計為1~40mg/m2 之附著量所形成的含有Zr之皮膜層。
[6]如[5]記載之容器用鋼板，其中前述鍍Ni層之Ni量係0.42~2.4g/m2 。
[7]如[5]或[6]記載之容器用鋼板，其中前述鍍Ni層之Co含有率係0.1~89ppm。
[8]如[5]~[7]中任1項記載之容器用鋼板，其中前述含有Zr之皮膜層的Zr換算附著量係1~37mg/m2 。
依據本發明，可得耐蝕性優異，且與經積層之樹脂薄膜的密著性及熔接性優異之容器用鋼板。
圖式簡單說明
第1圖係顯示鍍Ni中之Co濃度與穿孔蝕深度之關係的圖表。
第2圖係顯示鍍Ni-Co腐蝕狀況之一例，第2(a)圖係顯示SE(掃描式電子顯微鏡)影像、及第2(b)圖係顯示該鍍Ni-Co之腐蝕行為(推定)的模式截面圖。
第3圖係顯示鍍Ni腐蝕狀況之一例，第3(a)圖係顯示SE影像、及第3(b)圖係顯示該鍍Ni之腐蝕行為(推定)的模式截面圖。
 用以實施發明之形態
以下，詳細地說明本發明之實施形態的耐蝕性、密著性、熔接性優異之容器用鋼板。
本實施形態之容器用鋼板係具有鋼板、於鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co的鍍Ni層、及於鍍Ni層表面所形成之鉻酸鹽皮膜層或含有Zr之皮膜層所構成。
鉻酸鹽皮膜層係以Cr換算量計為1~40mg/m2 之附著量形成於鍍Ni層上。又，含有Zr之皮膜層係以Zr量計為1~40mg/m2 之附著量形成於鍍Ni層上。
鋼板係容器用鋼板之鍍敷原板，可例示如，由通常之鋼片製造步驟經過熱軋、酸洗、冷軋、退火、調質軋壓等步驟所製造的鋼板。
為了確保耐蝕性、密著性、熔接性，於作為鍍敷原板之鋼板，形成微量含有Co之鍍Ni層。Ni係兼具有對鋼板之密著性與鍛接性(以熔點以下之溫度接合的特性)的金屬，藉將以Ni量計為0.3g/m2 以上作為於鋼板施行鍍Ni時的附著量，即開始發揮實用之密著性或熔接性。於更增加鍍Ni之附著量時，密著性或熔接性提升，但於附著量大於3g/m2 時，密著性及熔接性之提升效果飽和，於工業上無利益。因此，鍍Ni層之附著量需為0.3~3g/m2 。
又，於鍍Ni層中之Co含有率過低時，腐蝕之進行方向係鋼板之板厚方向，穿孔腐蝕加劇而不佳。藉使鍍Ni層中之Co含有率為0.1ppm以上，腐蝕將沿著鍍Ni層與基質鐵之界面開始進行。另一方面，於鍍Ni層中之Co含有率過剩時，Ni之鍛接性受到阻礙，結果，熔接性劣化。因此，鍍Ni層中之Co含有率需為100ppm以下。
又，於鍍Ni層除了Co以外，亦含有不可避免的雜質及其餘之Ni。
於鋼板形成前述含有Co之鍍Ni層的方法，係於由硫酸鎳或氯化鎳所構成之眾所周知的酸性鎳鍍敷溶液，將溶解有硫酸鈷或氯化鈷之溶液作為電鍍浴，進行陰極電解之方法，於工業上係有用，但並未特別地限定於該等方法。
於鍍Ni層上進行鉻酸鹽處理，以提升耐蝕性、與樹脂薄膜之密著性，特別是加工後之二次密著性。藉由鉻酸鹽處理，形成由水合氧化Cr所構成之鉻酸鹽皮膜、或由水合氧化Cr與金屬Cr所構成之鉻酸鹽皮膜。
構成鉻酸鹽皮膜層之金屬Cr或水合氧化Cr因具有優異之化學穩定性，故與鉻酸鹽皮膜量成比例地提升容器用鋼板之耐蝕性。又，水合氧化Cr藉與樹脂薄膜之官能基形成堅固之化學鍵，於加熱水蒸氣環境氣體下亦發揮優異之密著性，鉻酸鹽皮膜層之附著量越多，越可提升與樹脂薄膜之密著性。於實用上，為發揮充分之耐蝕性及密著性，需要以金屬Cr換算量計為1mg/m2 以上的鉻酸鹽皮膜層。
藉鉻酸鹽皮膜層之附著量的增加，耐蝕性、密著性之提升效果亦增大，但因鉻酸鹽皮膜層中之水合氧化Cr係電絕緣體，於鉻酸鹽被膜層之附著量增大時，容器用鋼板之電阻變得非常高，成為造成熔接性劣化的要因。具體而言，於鉻酸鹽皮膜層之附著量以金屬Cr換算計大於40mg/m2 時，熔接性極為劣化。因此，鉻酸鹽皮膜層之附著量以金屬Cr換算計需為40mg/m2 以下。
鉻酸鹽處理方法亦可以利用各種Cr酸之鈉鹽、鉀鹽、銨鹽的水溶液進行之浸漬處理、噴霧處理、電解處理等任一方法進行。於Cr酸添加有作為助電鍍劑之硫酸離子、氟化物離子(包含錯離子)或該等之混合物的水溶液中，施行陰極電解處理於工業上亦為佳。
又，亦可於鍍Ni層形成含有Zr之皮膜層取代前述鉻酸鹽皮膜層。含有Zr之皮膜層係由氧化Zr、磷酸Zr、氫氧化Zr、氟化Zr等Zr化合物所構成的皮膜或該等之複合皮膜。於以1mg/m2 以上之附著量作為金屬Zr量，形成含有Zr之皮膜層時，發現與前述鉻酸鹽皮膜層同樣地，與樹脂薄膜之密著性或耐蝕性飛躍性地提升。另一方面，於含有Zr之皮膜層之附著量以金屬Zr量計大於40mg/m2 時，熔接性及外觀性劣化。特別是，因Zr皮膜層為電絕緣體，故電阻非常地高，而成為造成熔接性劣化的要因，於附著量以金屬Zr換算計大於40mg/m2 時，熔接性極為劣化。因此，Zr皮膜層之附著量以金屬Zr量計需為1~40mg/m2 。
於使用鉻酸鹽皮膜層之本發明態樣中，以下述範圍為佳。
鍍Ni層之Ni量(g/m2 )：0.35~2.8(更佳為0.6~2.4；特佳係0.8~1.8)
鍍Ni層之Co含有率(ppm)：0.3~92(更佳為0.3~25；特佳係0.3~24)
鉻酸鹽皮膜層之Cr換算附著量(mg/m2 )：1.2~38(更佳為4~22；特佳係5~22)
形成含有Zr之皮膜層的方法，可使用例如，將形成鍍Ni層後之鋼板於以氟化Zr、磷酸Zr、氫氟酸作為主成分之酸性溶液中進行浸漬處理、或陰極電解處理方法等。
於使用含有Zr之皮膜層的本發明態樣中，以下述範圍為佳。
鍍Ni層之Ni量(g/m2 )：0.42~2.4(更佳為0.8~2.4；特佳係1.1~2.4)
鍍Ni層之Co含有率(ppm)：0.1~89(更佳為0.2~89；特佳係0.2~47)
含有Zr之皮膜層的Zr換算附著量(mg/m2 )：1~37(更佳為12~37；特佳係12~28)
依據本實施形態，可提升容器用鋼板之耐穿孔腐蝕性，並提高熔接性、對樹脂薄膜之密著性及對加工後之樹脂薄膜的密著性。
實施例
藉由實施例更加詳細地說明本發明。
首先，敘述本發明之實施例及比較例，於表1顯示該結果。利用以下(1)所示之方法製作試料，並針對(2)之(A)~(D)各項目進行性能評價。
(1)試料製作方法 鋼板(鍍敷原板)：
使用板厚0.2mm之調質度(Temper Grade)3(T-3)的鍍錫鐵皮(tinplate)用冷軋鋼板作為鍍敷原板。
鍍Ni條件：
於包含濃度20%之硫酸鎳、濃度15%之氯化鎢、1%之硼酸，且調整至pH=2的水溶液中添加0.1~1%之硫酸鈷，並以5A/dm2 進行陰極電解，於鋼板形成鍍Ni層。Ni附著量係以電解時間控制。
鉻酸鹽處理條件：
於包含濃度10%之氧化鉻(VI)、濃度0.2%之硫酸、濃度0.1%之氟化銨的水溶液中，進行10A/dm2 之陰極電解，並水洗10秒鐘，於鍍Ni層形成鉻酸鹽皮膜層。鉻酸鹽皮膜層之Cr附著量係以電解時間控制。
含有Zr之皮膜層的處理條件：
於濃度5%之氟化鋯、濃度4%之磷酸、濃度5%之氫氟酸的水溶液中，進行10A/dm2 之陰極電解，於鍍Ni層形成含有Zr之皮膜層。含有Zr之皮膜層的Zr附著量係以電解時間控制。
<鍍敷量之測定方法>
Ni、Zr、Cr量之測定係以螢光X射線測定。Co係使鍍敷層溶解於10%之鹽酸，再藉由原子吸光分析測定Co濃度，並算出。
(2)試料評價方法 (A)熔接性
於試驗片積層厚度15μm之PET薄膜，以重疊邊限0.5mm、加壓力45kgf、熔接金屬線速度80m/min之條件變更電流，實施熔接，由以可得充分之熔接強度的最小電流值、及散射等熔接缺陷開始變得醒目之最大電流值所構成的最適電流範圍之大小、及熔接穩定狀態，總合地判斷最適熔接條件之範圍，以4階段(◎：非常寬廣、○：寬廣、△：於實用上無問題、×：狹窄)評價。
(B)密著性
於試料積層15μm厚之PET薄膜，以DrD壓製作杯。以DI機器將該杯成形成DI罐。觀察成形後之DI罐的罐壁部之薄膜剝離狀況，總合地以4階段(◎：完全無剝離、○：有些微之薄膜浮起、△：有大之剝離、×：薄膜於DI成形中剝離，造成外殼破裂)進行評價。
(C)二次密著性
於試料積層15μm厚之PET薄膜，以DrD壓製作杯。以DI機器將該杯成形成DI罐後，以大於PET薄膜之熔點的溫度(240℃左右)進行10分鐘之熱處理，再於125℃、30分鐘之加熱水蒸氣氣體環境下進行處理(蒸餾處理)。之後，觀察蒸餾處理後之DI罐的罐壁部之薄膜剝離狀況，總合地以4段階(◎：完全無剝離、○：有些微之薄膜浮起、△：有大之剝離、×：薄膜於DI成形中剝離，造成外殼破裂)進行評價。
(D)耐蝕性
製作積層有PET薄膜之熔接罐，於熔接部分塗布修補塗料，並將由1.5%檸檬酸-1.5%食鹽混合液所構成之試驗液填充於熔接罐，蓋上蓋子，以55℃安置於恆溫室1個月。之後，以4段階判斷熔接罐內部之薄膜受損部位的腐蝕狀況(◎：無穿孔腐蝕、○：有些微於實用上無問題左右之穿孔腐蝕、△：有進行穿孔腐蝕、×：因穿孔腐蝕而產生開孔)並進行評價。又，以光學顯微鏡觀察10處腐蝕處，測定腐蝕深度之平均值。
對變更有鍍Ni之附著量、Co含有率、鉻酸鹽皮膜層或含有Zr之皮膜層的實施例1~11及比較例1~7，於表1顯示熔接性、密著性、二次密著性及耐蝕性之評價結果。於表1中為本發明範圍外之數值畫有底線。
如表1所示，可知實施例1~11之鋼板均為熔接性、密著性、二次密著性及耐蝕性優異。
比較例1因鍍Ni層之附著量低，故熔接性與耐蝕性特別低下。
比較例2、3之鍍Ni層中的Co含有率為本發明之範圍外，比較例2中耐蝕性、比較例3中熔接性分別低下。
比較例4、5之鉻酸鹽皮膜層之附著量為本發明之範圍外，比較例4中二次密著性、比較例5中熔接性分別低下。
比較例6、7之含有Zr之皮膜層之附著量為本發明之範圍外，比較例6中二次密著性、比較例7中熔接性分別低下。
接著，準備複數板厚0.2mm之調質度3(T-3)的鍍錫鐵皮用冷軋鋼板作為鍍敷原板，以於前述相同之鍍Ni條件進行電鍍，於各鋼板形成有鍍Ni層。將Ni附著量統一為0.7g/m2 。
然後，於與前述相同之鉻酸鹽處理條件下，於鍍Ni層形成鉻酸鹽皮膜層。將鉻酸鹽皮膜層之Cr附著量統一為8g/m2 。
對所得之各種鋼板，與前述同樣地進行耐蝕性試驗，測定穿孔腐蝕之深度。於第1圖顯示結果。
如第1圖所示，鍍Ni層中之Co含有率係0.1~100ppm之範圍，穿孔蝕深度係0.02~0.08mm之範圍，可知對穿孔腐蝕之耐蝕性大幅地提升。於Co含有率為0.1~100ppm之範圍，腐蝕沿著鍍Ni層與基質鐵之界面進行。另一方面，於Co含有率小於0.1ppm之範圍，腐蝕沿著鋼板之厚度方向進行。
第1圖係顯示鍍Ni中之Co濃度與穿孔蝕深度之關係的圖表。
第2圖係顯示鍍Ni-Co腐蝕狀況之一例，第2(a)圖係顯示SE(掃描式電子顯微鏡)影像、及第2(b)圖係顯示該鍍Ni-Co之腐蝕行為(推定)的模式截面圖。
第3圖係顯示鍍Ni腐蝕狀況之一例，第3(a)圖係顯示SE影像、及第3(b)圖係顯示該鍍Ni之腐蝕行為(推定)的模式截面圖。

Claims (8)

  1. 密著性、熔接性優異之使用於2片罐及3片罐之容器用積層鋼板，其特徵在於具有以下而成者：鋼板；鍍Ni層，係於前述鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co者；及鉻酸鹽皮膜層，係於前述鍍Ni層表面以Cr換算量計為1~40mg/m2 之附著量所形成者。
  2. 如申請專利範圍第1項之容器用積層鋼板，其中前述鍍Ni層之Ni量係0.35~2.8g/m2 。
  3. 如申請專利範圍第1或2項之容器用積層鋼板，其中前述鍍Ni層之Co含有率係0.3~92ppm。
  4. 如申請專利範圍第1或2項之容器用積層鋼板，其中前述鉻酸鹽皮膜層之Cr換算附著量係1.2~38mg/m2 。
  5. 密著性、熔接性優異之使用於2片罐及3片罐之容器用積層鋼板，其特徵在於具有以下而成者：鋼板；鍍Ni層，係於前述鋼板表面以Ni量計為0.3~3g/m2 之附著量所形成，且於0.1~100ppm之範圍包含Co者；及含有Zr之皮膜層，係於前述鍍Ni層表面以Zr量計為1~40mg/m2 之附著量所形成者。
  6. 如申請專利範圍第5項之容器用積層鋼板，其中前述鍍Ni層之Ni量係0.42~2.4g/m2 。
  7. 如申請專利範圍第5或6項之容器用積層鋼板，其中前述 鍍Ni層之Co含有率係0.1~89ppm。
  8. 如申請專利範圍第5或6項之容器用積層鋼板，其中前述含有Zr之皮膜層的Zr換算附著量係1~37mg/m2 。
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