WO2018117759A2 - 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물 - Google Patents

실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물 Download PDF

Info

Publication number
WO2018117759A2
WO2018117759A2 PCT/KR2017/015402 KR2017015402W WO2018117759A2 WO 2018117759 A2 WO2018117759 A2 WO 2018117759A2 KR 2017015402 W KR2017015402 W KR 2017015402W WO 2018117759 A2 WO2018117759 A2 WO 2018117759A2
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
post
group
oxide
film
Prior art date
Application number
PCT/KR2017/015402
Other languages
English (en)
French (fr)
Other versions
WO2018117759A3 (ko
Inventor
김연호
김용운
김영근
송연균
Original Assignee
주식회사 포스코
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 포스코 filed Critical 주식회사 포스코
Priority to JP2019533459A priority Critical patent/JP6850889B2/ja
Priority to CN201780080160.3A priority patent/CN110121570B/zh
Priority to US16/471,889 priority patent/US11299639B2/en
Priority to EP17882913.1A priority patent/EP3561145A4/en
Publication of WO2018117759A2 publication Critical patent/WO2018117759A2/ko
Publication of WO2018117759A3 publication Critical patent/WO2018117759A3/ko

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—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
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/406—Oxides of iron group metals
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide 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
    • 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
    • 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
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • 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
    • 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
    • Y10T428/12569—Synthetic resin
    • 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
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • 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
    • Y10T428/12597—Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
    • 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
    • Y10T428/12597—Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
    • Y10T428/12604—Film [e.g., glaze, etc.]
    • 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
    • Y10T428/12611—Oxide-containing component
    • 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
    • Y10T428/12611—Oxide-containing component
    • Y10T428/12618—Plural oxides
    • 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
    • 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
    • Y10T428/12667—Oxide of transition metal or Al
    • 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
    • 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
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • 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
    • 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
    • Y10T428/12958—Next to Fe-base component
    • 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]
    • 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]
    • Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
    • 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.]
    • 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.]
    • 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

Definitions

  • the present invention relates to a zinc-based plated steel material having excellent sealer adhesion and a composition for forming a post-treatment film.
  • Zinc-based galvanized steel sheet used as automotive plate material is inexpensive, excellent corrosion resistance, and the surface appearance is beautiful, the usage is gradually increasing for automotive interior and exterior plates.
  • the plated steel sheet is subjected to an assembly process such as press forming process, welding and bonding, degreasing process, phosphate treatment process and painting process in an automobile manufacturing process, in which case the galvanized steel sheet is lubricated, weldable, adhesive, coated, etc. The same properties are required.
  • Zinc-based galvanized steel sheet has different physical properties depending on the composition and manufacturing method of the plated layer formed on the steel sheet and needs to be compensated for the poor physical properties.
  • GI hot-dip galvanized steel sheet
  • EG electro-galvanized steel sheet
  • the plating layer is detached and welded to the bead part of the die during press molding accompanied by high pressure and high speed friction. There is. This causes defects such as scratches and dents on the surface of the steel sheet.
  • the surface of the zinc-based galvanized steel sheet used as an automobile plate is required to be post-treated, thereby improving thermal properties.
  • Patent Document 1 discloses a technique of forming a phosphate layer on the surface of a zinc plated layer
  • Patent Document 2 discloses a technique of forming a metal oxide layer on a surface of a zinc plated layer.
  • the technique of forming the phosphate layer requires a process such as surface adjustment, phosphate treatment, washing with water, drying, etc., and requires substantial facility space and solution management during actual operation, and is a treatment method that depends on the reactivity with the plating layer. There is a need to change the solution composition according to the type of interlinked steel sheet.
  • the technique of forming the metal oxide layer has a problem that can not be applied to all zinc-based galvanized steel sheet because it is limited by the plating layer metal components.
  • Patent Document 1 Korean Unexamined Patent Publication No. 10-2001-0074527
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2014-185381
  • One of the various objectives of this invention is providing the galvanized steel material excellent in sealer adhesiveness, and the composition for post-processing film formation.
  • An aspect of the present invention includes a base iron and a zinc-based plating layer sequentially formed on the base iron and a post-treatment coating, wherein the post-treatment coating is formed of at least one group A element selected from B, Al, V and Fe.
  • Oxide or oxide salt and an organic compound the content of oxygen atoms in the post-treatment film is 50 atomic% or more, the mole number of oxygen atoms covalently bonded with hydrogen in the post-treatment film is a, and shared with hydrogen
  • the number of moles of oxygen atoms not bonded is b, a zinc-based plated steel having a / b of 0.3 or more is provided.
  • Another aspect of the present invention includes an organic compound and an oxide or oxide salt of at least one group A element selected from B, Al, V and Fe, the content of oxygen atoms is 50 atomic% or more, and the covalent bond with hydrogen
  • the number of moles of oxygen atoms to be formed is a
  • the number of moles of oxygen atoms which do not form a covalent bond with hydrogen is b
  • a composition for forming a post-treatment film having a / b of 0.3 or more is provided.
  • the zinc-based plated steel material having a post-treatment coating according to the present invention has an advantage of excellent sealer adhesion.
  • the post-treatment film-forming composition according to the present invention has an advantage that can be applied regardless of the type of the plating layer.
  • zinc-plated steel is used as automotive steel, and the zinc-based galvanized steel is subjected to a press molding process, an assembly process such as welding and bonding, a degreasing process, a phosphate treatment process, and a painting process in a car manufacturing process.
  • zinc-based galvanized steel used as automotive steels is required to have excellent physical properties such as press workability, weldability, sealer adhesiveness, and the like. If the press workability is insufficient, the plating layer may stick to the mold or the material itself may break in the press forming process. If the weldability is insufficient, the welding electrode may be contaminated in the assembly process, resulting in electrode life and continuous spotting. This is because the number can be reduced, and if the sealer adhesiveness is insufficient, problems may occur in the strength of the bonded portion.
  • a post-treatment film is generally formed on the zinc-based plated steel.
  • the post-treatment film is required to have excellent film removal properties as well as the above properties. do. This is because when the film removal property is insufficient, the post-treatment coating may not be sufficiently removed in the degreasing process, which may cause a defect in the subsequent phosphate treatment and painting process, and consequently, the paintability may be reduced.
  • the inventors of the present invention have studied in depth to provide a composition for forming a post-treatment film having excellent press formability, weldability, sealer adhesion, and film removal property, and a zinc-based plated steel material having the post-treatment film formed thereon. As a result, the present invention has been completed.
  • the zinc-based plated steel having excellent sealer adhesion which is an aspect of the present invention, includes a base iron and a zinc-based plating layer sequentially formed on the base iron and a post-treatment coating.
  • the specific type and shape of the base iron is not particularly limited, and may be, for example, a hot rolled steel sheet, a cold rolled steel sheet, or a steel wire.
  • the specific type of the zinc-based plating layer is not particularly limited, and may be any one of a hot dip galvanized layer, an alloyed hot dip galvanized layer, an electrogalvanized layer, and a zinc deposited layer by PVD.
  • the type and component range of the alloying elements included in the zinc-based plating layer are not particularly limited.
  • the zinc-based plating layer may include an appropriate amount of elements such as Al, Mg, and Si in addition to Zn. .
  • the post-treatment coating includes an oxide or oxide salt of at least one group A element selected from B, Al, V and Fe and an organic compound, and if necessary, an oxide of at least one group B element selected from Mn, Mo and W. Or oxide salts.
  • group A element selected from B, Al, V and Fe
  • organic compound if necessary, an oxide of at least one group B element selected from Mn, Mo and W.
  • oxide salts if necessary, an oxide of at least one group B element selected from Mn, Mo and W.
  • each component which comprises a post-processing film is demonstrated in detail.
  • the oxide or oxide salt of the group A element serves to improve the adhesion with the sealer applied on the after-treatment film.
  • the group A element means at least one element selected from B, Al, V and Fe.
  • the group A element in the after-treatment film may include 1 mol / kg or more. If the group A element is less than 1 mol / kg, there is a concern that the adhesive strength between the after-treatment film and the sealer may not be sufficient.
  • the present invention is not particularly limited to specific types of oxides or oxide salts of group A elements.
  • group A elements are boron (B)
  • the oxides or oxide salts of group A elements may be boric acid, borax, or the like.
  • the oxide or oxide salt of the group A element may have at least one or more hydroxyl groups in the aqueous solution of pH 4-7 range, in this case, it may be advantageous to improve the sealer adhesion of the after-treatment film.
  • the oxide or oxide salt of the group B element may play a role of enhancing the adhesion between the after-treatment film and the material, but in the present invention, even if it is not added, there is no big problem in securing the desired sealer adhesion.
  • the group B element means at least one element selected from Mn, Mo, and W.
  • the group B element in the after-treatment film may be included in an amount of 3.5 mol / kg or less. If the content of the group B element exceeds 3.5 mol / kg, the content of the group A element is relatively decreased, resulting in a decrease in the sealer adhesiveness, and an increase in adhesion to the material, thereby deteriorating the film removal properties of the after-treatment film. There is a concern.
  • the specific type of the oxide or oxide salt of the group B element is not particularly limited.
  • the oxide or oxide salt of the group B element is ammonium molybdate or phosphomolybdic acid. Sodium, sodium molybdate, and the like.
  • the organic compound serves as a binder for stably presenting oxides or oxide salts in the after-treatment coating, and contributes in part to improving sealer adhesion.
  • the content of the organic compound is not particularly limited, but according to an exemplary embodiment, the organic compound may be included in an amount of 5 parts by weight to 30 parts by weight based on 100 parts by weight of the after-treatment film. If less than 5 parts by weight, film stability to sealer adhesion may be inferior. On the other hand, if it exceeds 30 parts by weight, it may be advantageous in terms of sealer adhesion.
  • the interlinked steels may stick together, and in severe cases, the removal of the post-treatment coating may be insufficient in the degreasing process of the automobile assembly process, which may cause defects in the subsequent phosphate treatment and painting processes.
  • the organic compound may have at least one hydroxyl group or carboxyl group, and more specifically, polyvinylacetate (PVAc), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl butyral (PVB ) And polyethylene glycol (PEG).
  • PVAc polyvinylacetate
  • PVA polyvinyl alcohol
  • PAA polyacrylic acid
  • PVB polyvinyl butyral
  • PEG polyethylene glycol
  • Zinc-based plated steel having excellent sealer adhesiveness which is an aspect of the present invention, is characterized in that the content of oxygen atoms in the after-treatment coating is 50 atomic% or more. If the content of oxygen atoms is less than 50 atomic%, the adhesion of the zinc-based plated steel and the sealer may be deteriorated due to insufficient amount of hydroxyl groups serving as a binding site by contributing to the improvement of adhesion with the sealer. .
  • the content of oxygen atoms in the after-treatment film is a value measured or calculated considering only components and oxygen in the after-treatment film, except for the plating layer component and hydrogen, and is contaminated by acetone degreasing of the zinc-based plated steel on which the after-treatment film is formed.
  • After removal of the rust preventive oil can be measured using X-ray Photoelectron Spectroscopy (XPS) analysis.
  • XPS X-ray Photoelectron Spectroscopy
  • the reason for excluding the plated layer component when calculating the oxygen content is that the composition for post-treatment film formation of the present invention has little reactivity with the plated layer, and if the post-treatment film-forming composition reacts with the plated layer component, the plated layer component is post-treated.
  • the content of the plating layer component should also be considered.
  • the more preferable range of the content of oxygen atoms in the film-forming composition is 55 atomic% or more, and even more preferred range is 60 atomic% or more.
  • a zinc-based plated steel having excellent sealer adhesion refers to the number of moles of oxygen atoms covalently bonded to hydrogen in the oxygen atoms in the after-treatment film, a, and that of oxygen atoms not covalently bonded to hydrogen.
  • a / b is 0.3 or more. If a / b is less than 0.3, the amount of hydroxyl groups serving as a binding site due to the improvement of adhesion with the sealer is insufficient, and thus the adhesion strength between the zinc-based plated steel and the sealer may be deteriorated. The higher the value of a / b, the better the sealer adhesion.
  • the upper limit thereof is not particularly limited in the present invention.
  • the value when the value is too large, it may be disadvantageous in terms of adhesion to the material and film stability.
  • the upper limit can be limited to ten.
  • a / b is the acetone degreasing of the zinc-based galvanized steel on which the after-treatment film is formed to remove contamination or rust preventive oil, and then the binding energy peak of oxygen measured using XPS (X-ray Photoelectron Spectroscopy) analysis method. Obtained through curve fitting.
  • the more preferable ranges of a / b are 1.0 or more and 9.0 or less, and even more preferable ranges are 2.0 or more and 8.0 or less.
  • the after-treatment coating of the zinc-based plated steel having excellent sealer adhesion of the present invention includes an oxide or an oxide salt of the Group B element, it has at least one hydroxyl group in an aqueous solution of pH 4-7.
  • c / d may be 0.5 or more. In this case, it may be advantageous to improve the sealer adhesion of the after-treatment coating.
  • the present invention is not particularly limited to the upper limit, but if the value is too large may be disadvantageous in terms of adhesion to the material and film stability, this In consideration, the upper limit can be limited to 100.
  • the more preferable ranges of c / d are 2.0 or more and 50 or less, and even more preferable ranges are 5.0 or more and 30 or less.
  • the specific method for forming the post-treatment coating is not particularly limited, but according to an example, the post-treatment coating may be a dry coating method such as PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition) It may be formed by a powder spray coating method such as coating, a solution coating method such as roll coating, but when formed by a double solution coating method, there is an advantage in that the process is simple and the process operation cost is low.
  • a dry coating method such as PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition)
  • a powder spray coating method such as coating
  • a solution coating method such as roll coating
  • coating it is necessary to control the drying temperature at the time of drying after application
  • the coating amount of the post-treatment coating is not particularly limited, but according to an exemplary embodiment, the coating amount of the post-treatment coating may be 100 mg / m 2 to 1000 mg / m 2 . If the coating amount is less than 100 mg / m 2 , the post-treatment film may be unevenly formed due to the roughness of the material itself. On the other hand, if the coating amount is more than 1000 mg / m 2 , the manufacturing cost increases and the drying may be insufficient. There is.
  • composition for post-processing film formation which is another aspect of this invention excellent in sealer adhesiveness is demonstrated in detail.
  • the post-treatment film-forming composition which is another aspect of the present invention, includes an organic compound and an oxide or oxide salt of at least one group A element selected from B, Al, V, and Fe.
  • Mn It may include an oxide or an oxide salt of at least one B group element selected from Mo, and W.
  • the present invention does not exclude the addition of other effective ingredients than the above components, for example, may further include a leveling agent and the like.
  • the film-forming composition of the present invention may be provided in the form of a solution in which the following components are dissolved in a solvent such as water, it may also be provided in the form of a powder in which the following components are simply mixed. If the composition for forming a film of the present invention is provided in the form of a solution, the content of each component, the content of oxygen atoms, and the number-of-moles ratio of oxygen atoms described below are based on only nonvolatile solids except for solvents such as water. It corresponds to the measured value.
  • the film-forming composition of the present invention is characterized in that the content of oxygen atoms is 50 atomic% or more.
  • the reason for controlling the content of oxygen atoms in the film-forming composition is as described above.
  • the content of oxygen atoms in the film-forming composition may be calculated from the molecular structure of specific components constituting the film-forming composition.
  • the film-forming composition of the present invention is characterized in that a / b is 0.3 or more when the mole number of oxygen atoms covalently bonded to hydrogen is a and the mole number of oxygen atoms covalently bonded to hydrogen is b. It is done.
  • the reason for controlling a / b in the above range is as described above.
  • a / b may be calculated from the molecular structure of specific components constituting the film-forming composition.
  • the pH of the film-forming composition is not particularly limited, but the pH is preferably 3.0 to 7.0 in order to form a stable film while preventing dissolution of the plating layer.
  • the oxygen content and a / b in the after-treatment film was measured, the results are shown in Table 1 together.
  • the oxygen content in the after-treatment film is an average value per unit depth of the nanometer scale measured by the x-ray photoelectron spectroscopy (XPS) analysis of the zinc-based plated steel on which the after-treatment film is formed, and a / b is measured by the XPS analysis method. It is the average value per unit depth obtained through the curve fitting of one oxygen binding energy peak.
  • XPS x-ray photoelectron spectroscopy
  • a cup drawing test was carried out.
  • the cup drawing test was performed using a tester composed of a mold and a punch, and the test was performed while increasing the BHF (Blank Holding Force) to maximize the BHF value immediately before breaking of the material. It shows in Table 1 as BHF value.
  • BHF Bit Holding Force
  • the film removal test was performed by stirring and immersing the material at 50 to 55 ° C. for 2 minutes using a degreasing solution used in the automobile manufacturing process, washing the material, and then measuring the amount of coating film remaining on the surface of the material to remove the amount of coating before degreasing.
  • the film rate is calculated as a percentage and is shown in Table 1.
  • the coating film residual amount was calculated by quantitatively analyzing the molybdenum content of the dissolved solution by ICP (Inductively Coupled Plasma) after dissolving the coating layer having a predetermined area with an acid solution.
  • the adhesive strength is less than 1.0 kgf / cm 2. It can be seen that.
  • the adhesive strength criterion is 1.0kgf / cm 2
  • the oxygen (O) content contained in the post-treatment film It is more preferable that it is 55 atomic% or more, and a / b is 1.0 or more.
  • the maximum BHF value and the film removal property showed excellent characteristics under all post-treatment film conditions regardless of the oxygen content or a / b in the film.
  • the maximum BHF value shows a higher value in Comparative Examples 1, 2, and Inventive Examples 1 to 12, in which the after-treatment film is formed, compared to the conventional example, which is an untreated material, which means that the workability is significantly improved when forming the after-treatment film.
  • a / b in the film is controlled by a large amount of oxide or oxide salt and a small amount of organic compound, but the present invention is not limited thereto.
  • the molecular structure of the organic compound composed of 30% by weight or less in the film is further limited. Of course, it can be controlled even with the ratio of the oxygen and the hydroxyl group present in the.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

소지철과 상기 소지철 상에 순차로 형성된 아연계 도금층 및 후처리 피막을 포함하고, 상기 후처리 피막은 B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하고, 상기 후처리 피막 내 산소 원자의 함량은 50원자% 이상이며, 상기 후처리 피막 내 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 아연계 도금 강재와 상기 후처리 피막 형성용 조성물이 개시된다.

Description

실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물
본 발명은 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물에 관한 것이다.
자동차 판재로 사용되는 아연계 도금강판은 가격이 저렴하고, 내식성이 우수하며, 표면외관이 미려하여 자동차 내·외판용으로 그 사용량이 점차 증가하고 있는 추세이다. 상기 도금강판은 자동차 제조공정에서 프레스 성형 공정, 용접 및 접착과 같은 조립 공정, 탈지 공정, 인산염 처리 공정 및 도장 공정을 순서대로 거치게 되는데, 이때 아연도금강판은 윤활성, 용접성, 접착성, 도장성 등과 같은 물성들이 요구된다.
아연계 도금강판은 강판 상에 형성된 도금층의 조성 및 제조방법에 따라 나타나는 물성이 상이하며 열위한 물성에 대해서는 보완이 필요하다. 예를 들어, 용융아연도금강판(GI) 및 전기아연도금강판(EG)의 경우, 연질의 도금층으로 인하여 고압 및 고속의 마찰을 동반하는 프레스 성형 시 도금층이 탈리되어 다이의 비드부 등에 융착되는 문제가 있다. 이로 인하여 강판의 표면에 스크래치나 덴트와 같은 결함을 유발하게 된다. 합금화 용융아연도금강판(GA)의 경우, 높은 표면 마찰계수로 인하여 프레스 성형 시 윤활특성이 불충분하여 소재 자체가 파단되거나 경한 도금층이 떨어져 나가는 파우더링 현상이 발생하는 문제가 있다. 이러한 이유로 상기 도금강판들은 후처리를 통한 윤활성 개선을 필요로 하게 되며, 윤활성 외에 용접성, 접착성, 도장성 등을 만족하여야 한다.
또한, 알루미늄(Al)이나 마그네슘(Mg) 등의 원소를 도금층에 포함하는 아연합금도금강판의 경우, 프레스 성형성은 우수하나, 극표층에 존재하는 안정한 금속산화물로 인하여 자동차 차체 조립공정에서 실러와의 접착성이 떨어지는 문제가 있다.
이와 같은 문제를 해결하기 위하여 자동차 판재로 사용되는 아연계 도금강판의 표면에는 후처리가 필요하며, 이를 통해 열위한 물성을 향상시킬 수 있다.
후처리에 관한 기술로서, 특허문헌 1에는 아연도금층 표면에 인산염층을 형성하는 기술이 제시되어 있으며, 특허문헌 2에는 아연도금층 표면에 금속산화물층을 형성하는 기술이 제시되어 있다. 그러나, 인산염층을 형성하는 기술은 표면조정, 인산염 처리, 수세, 건조 등의 과정이 필요하고, 실 조업 시 상당한 설비공간과 용액관리를 필요로 하며, 도금층과의 반응성에 의존하는 처리방법이므로 아연계 도금강판 종류에 따라 용액조성을 변경해야 하는 번거로움이 있다. 또한, 금속산화물층을 형성하는 기술은 도금층 금속 성분에 제한을 받기 때문에 모든 아연계 도금강판에 적용할 수 없는 문제가 있다.
(특허문헌 1) 한국 공개특허공보 제10-2001-0074527호
(특허문헌 2) 일본 공개특허공보 제2014-185381호
본 발명의 여러 목적 중 하나는, 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물을 제공하는 것이다.
본 발명의 일 측면은, 소지철과 상기 소지철 상에 순차로 형성된 아연계 도금층 및 후처리 피막을 포함하고, 상기 후처리 피막은 B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하고, 상기 후처리 피막 내 산소 원자의 함량은 50원자% 이상이며, 상기 후처리 피막 내 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 아연계 도금 강재를 제공한다.
본 발명의 다른 측면은, B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하고, 산소 원자의 함량은 50원자% 이상이며, 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 후처리 피막 형성용 조성물을 제공한다.
본 발명의 여러 효과 중 하나로서, 본 발명에 의해 후처리 피막이 형성된 아연계 도금 강재는 실러 접착성이 우수한 장점이 있다.
또한, 본 발명에 따른 후처리 피막 형성용 조성물은 도금층의 종류에 관계 없이 적용이 가능한 장점이 있다.
본 발명의 다양하면서도 유익한 장점과 효과는 상술한 내용에 한정되지 않으며, 본 발명의 구체적인 실시 형태를 설명하는 과정에서 보다 쉽게 이해될 수 있을 이다.
일반적으로 자동차용 강재로는 아연계 도금 강재가 이용되는데, 이러한 아연계 도금 강재는 자동차 제조 과정에서 프레스 성형 공정, 용접 및 접착과 같은 조립 공정, 탈지 공정, 인산염 처리 공정 및 도장 공정을 순차로 거치게 된다. 따라서, 자동차용 강재로 이용되는 아연계 도금 강재에는 프레스 가공성, 용접성, 실러(sealer) 접착성 등과 같은 물성이 우수할 것이 요구된다. 만약, 프레스 가공성이 불충분할 경우 프레스 성형 공정에서 도금층이 금형에 달라 붙거나 소재 자체가 파단되는 문제가 발생할 수 있으며, 용접성이 불충분할 경우 조립 공정에서 용접 전극에 오염이 발생해 전극 수명 및 연속 타점수가 저감될 수 있으며, 실러 접착성이 불충분할 경우 접착부 강도에 문제가 발생할 수 있기 때문이다.
이러한 이유로 일반적으로 아연계 도금 강재의 부족한 물성을 보완하기 위해, 아연계 도금 강재 상에 후처리 피막을 형성하게 되는데, 이러한 후처리 피막은 상기와 같은 물성뿐 아니라, 탈막성이 우수할 것이 추가적으로 요구된다. 이는 탈막성이 부족할 경우 탈지 공정에서 후처리 피막이 충분히 제거되지 못하고, 이로 인해 후속 공정인 인산염 처리 및 도장 공정에서 불량을 일으킬 수 있으며, 결과적으로 도장성이 저하될 수 있기 때문이다.
이러한 배경 하, 본 발명의 발명자들은 프레스 가공성, 용접성, 실러(sealer) 접착성 및 탈막성이 우수한 후처리 피막 형성용 조성물과 그 후처리 피막이 형성된 아연계 도금 강재를 제공하고자 깊이 있게 연구하였으며, 그 결과 본 발명을 완성하기에 이르렀다.
이하, 본 발명의 일 측면인 실러 접착성이 우수한 아연계 도금 강재에 대하여 상세히 설명한다.
본 발명의 일 측면인 실러 접착성이 우수한 아연계 도금 강재는 소지철과 상기 소지철 상에 순차로 형성된 아연계 도금층 및 후처리 피막을 포함한다. 본 발명에서는 소지철의 구체적인 종류 및 형상에 대해서는 특별히 한정하지 않으며, 예를 들어, 열연강판, 냉연강판, 또는 강선재일 수 있다. 또한, 본 발명에서는 아연계 도금층의 구체적인 종류에 대해 특별히 한정하지 않으며, 용융아연 도금층, 합금화 용융아연 도금층, 전기아연 도금층, PVD에 의한 아연 증착층 중 어느 하나일 수 있다. 한편, 본 발명에서는 아연계 도금층 내 포함된 합금 원소의 종류 및 성분 범위에 대해서는 특별히 한정하지 않으며, 예를 들어, 아연계 도금층은 Zn 외에도 Al, Mg, Si 등의 원소를 적정량 포함하고 있을 수 있다.
후처리 피막은 B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하며, 필요에 따라, Mn, Mo 및 W로부터 선택된 1종 이상의 B군 원소의 산화물 또는 산화물염을 포함할 수 있다. 이하에서는, 후처리 피막을 이루는 각 성분에 대하여 상세히 설명한다.
A군 원소의 산화물 또는 산화물염
A군 원소의 산화물 또는 산화물염은 후처리 피막 상에 도포되는 실러와의 접착성을 향상시키는 역할을 한다. 여기서, A군 원소는 B, Al, V 및 Fe로부터 선택된 1종 이상의 원소를 의미한다.
본 발명에서는 A군 원소의 산화물 또는 산화물염의 함량에 대해서는 특별히 한정하지 않는다. 다만, 제한되지 않는 일 예에 따르면, 후처리 피막 내 A군 원소는 1mol/kg 이상 포함될 수 있다. 만약, A군 원소가 1mol/kg 미만일 경우 후처리 피막과 실러와의 접착 강도가 충분치 못할 우려가 있다.
본 발명에서는 A군 원소의 산화물 또는 산화물염의 구체적인 종류에 대해서도 특별히 한정하지 않으나, 예를 들어, A군 원소가 보론(B)인 경우 A군 원소의 산화물 또는 산화물염은 붕산, 붕사 등일 수 있다.
일 예에 따르면, A군 원소의 산화물 또는 산화물염은 pH 4~7 범위의 수용액에서 적어도 1개 이상의 수산기를 가질 수 있으며, 이 경우, 후처리 피막의 실러 접착성 개선에 유리할 수 있다.
B군 원소의 산화물 또는 산화물염
B군 원소의 산화물 또는 산화물염은 후처리 피막과 소재와의 밀착성을 증진시키는 역할을 할 수 있으나, 본 발명에서는 이를 첨가하지 않더라도 목적하는 실러 접착성 확보에 큰 문제는 없다. 여기서, B군 원소는 Mn, Mo 및 W로부터 선택된 1종 이상의 원소를 의미한다.
본 발명에서는 B군 원소의 산화물 또는 산화물염의 함량에 대해서는 특별히 한정하지 않는다. 다만, 제한되지 않는 일 예에 따르면, 후처리 피막 내 B군 원소는 3.5mol/kg 이하로 포함될 수 있다. 만약, B군 원소의 함량이 3.5mol/kg을 초과할 경우 상대적으로 A군 원소의 함량이 감소하여 실러 접착성이 저하될 뿐만 아니라, 소재와의 밀착성이 증가하여 후처리 피막의 탈막성이 열화될 우려가 있다.
본 발명에서는 B군 원소의 산화물 또는 산화물염의 구체적인 종류에 대해서도 특별히 한정하지 않으나, 예를 들어, B군 원소가 몰리브덴(Mo)인 경우 B군 원소의 산화물 또는 산화물염은 몰리브덴산암모늄, 인몰리브덴산나트륨, 몰리브덴산나트륨 등 일 수 있다.
유기 화합물
유기 화합물은 후처리 피막 내 산화물 또는 산화물염이 안정하게 존재하도록 하는 바인더 역할을 하며, 실러 접착성 개선에도 일부 기여한다.
본 발명에서는 유기 화합물의 함량에 대해서는 특별히 한정하지 않으나, 제한되지 않는 일 예에 따르면, 후처리 피막 100중량부에 대하여 유기화합물은 5중량부 내지 30중량부로 포함될 수 있다. 만약, 5중량부 미만일 경우 피막 안정성 내지 실러 접착성이 열위할 수 있으며, 반면, 30중량부를 초과할 경우 실러 접착성 측면에서는 유리할 수 있으나, 그 자체가 접착제 역할을 할 수 있기 때문에 코일 상태의 아연계 도금 강재가 서로 달라 붙는 문제가 발생할 수 있으며, 심할 경우 자동차 조립 공정 중 탈지 공정에서 후처리 피막의 제거가 불충분하여 후속 공정인 인산염 처리 공정 및 도장 공정시 불량을 일으킬 수 있다.
일 예에 따르면, 유기 화합물은 적어도 1개 이상의 수산기 혹은 카르복시기를 가질 수 있으며, 보다 구체적으로, 폴리비닐아세테이트(PVAc), 폴리비닐알콜(PVA), 폴리아크릴산(PAA), 폴리비닐부티랄(PVB) 및 폴리에틸렌글리콜(PEG)로부터 선택된 1종 이상일 수 있다. 이 경우, 피막 안정성 및 실러 접착성 개선에 유리할 수 있다.
이하에서는, 후처리 피막이 가지는 기타 특징에 대하여 상세히 설명한다.
본 발명의 일 측면인 실러 접착성이 우수한 아연계 도금 강재는 후처리 피막 내 산소 원자의 함량이 50원자% 이상인 것을 특징으로 한다. 만약, 산소 원자의 함량이 50원자% 미만인 경우 실러와의 접착성 개선에 기여하여 결합 사이트로 작용하는 하이드록시기의 양이 부족하여, 아연계 도금 강재와 실러와의 접착강도가 열화될 수 있다. 여기서, 후처리 피막 내 산소 원자의 함량이란 도금층 성분 및 수소를 제외하고, 후처리 피막 내 성분과 산소만을 고려하여 측정 또는 산출된 값으로써, 후처리 피막이 형성된 아연계 도금 강재를 아세톤 탈지하여 오염이나 방청유를 제거한 후, XPS (X-ray Photoelectron Spectroscopy) 분석법을 이용하여 측정할 수 있다. 여기서, 산소 함량 산출시 도금층 성분을 제외하는 이유는 본 발명의 후처리 피막 형성용 조성물은 도금층과의 반응성이 거의 없기 때문이며, 만일 후처리 피막 형성용 조성물이 도금층 성분과 반응하여 도금층 성분이 후처리 피막 성분에 관여하는 경우에는 도금층 성분의 함량도 고려하여 계산하여야 함은 물론이다. 한편, 피막 형성용 조성물 내 산소 원자의 함량의 보다 바람직한 범위는 55원자% 이상이고, 보다 더 바람직한 범위는 60원자% 이상이다.
또한, 본 발명의 일 측면인 실러 접착성이 우수한 아연계 도금강재는 후처리 피막 내 산소 원자 중 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 것을 특징으로 한다. 만약, a/b가 0.3 미만일 경우 실러와의 접착성 개선에 기여하여 결합 사이트로 작용하는 하이드록시기의 양이 부족하여, 아연계 도금 강재와 실러와의 접착강도가 열화될 수 있다. a/b의 값이 클수록 실러 접착성 향상에 유리하기 때문에 본 발명에서는 그 상한에 대해서는 특별히 한정하지 않으나, 그 값이 지나치게 클 경우 소재와의 밀착성 및 피막 안정성 측면에서 불리할 수 있는 바, 이를 고려하여 그 상한을 10으로 한정할 수는 있다. 이때, a/b는 후처리 피막이 형성된 아연계 도금 강재를 아세톤 탈지하여 오염이나 방청유를 제거한 후, XPS (X-ray Photoelectron Spectroscopy) 분석법을 이용하여 측정한 산소의 결합 에너지 피크 (binding energy peak)의 곡선 맞춤 (curve fitting)을 통해 구할 수 있다. 한편, a/b의 보다 바람직한 범위는 1.0 이상 9.0 이하이며, 보다 더 바람직한 범위는 2.0 이상 8.0 이하이다.
일 예에 따르면, 본 발명의 실러 접착성이 우수한 아연계 도금 강재의 후처리 피막이 B군 원소의 산화물 또는 산화물염을 포함하는 경우에, pH 4~7 범위의 수용액에서 적어도 1개 이상의 수산기를 가지는 A군 원소의 몰수를 c라 하고, B군 원소의 몰수를 d라 할 때, c/d는 0.5 이상일 수 있다. 이 경우, 후처리 피막의 실러 접착성 개선에 유리할 수 있다. 한편, c/d 값이 클수록 실러 접착성 개선에 유리한 바, 본 발명에서는 그 상한에 대해서는 특별히 한정하지 않으나, 그 값이 지나치게 클 경우 소재와의 밀착성 및 피막 안정성 측면에서 불리할 수 있는 바, 이를 고려하여 그 상한을 100으로 한정할 수는 있다. 한편, c/d의 보다 바람직한 범위는 2.0 이상 50 이하이고, 보다 더 바람직한 범위는 5.0 이상 30 이하이다.
본 발명에서는 후처리 피막을 형성하는 구체적인 방법에 대해서는 특별히 한정하지 않으나, 제한되지 않는 일 예에 따르면, 후처리 피막은 PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition)와 같은 건식 코팅법, 용사코팅과 같은 분말 분사 코팅법, 롤코팅과 같은 용액도포법 등에 의해 형성될 수 있으나, 이중 용액도포법에 의해 형성할 경우 공정이 간단하고 공정 운영 비용이 저렴한 장점이 있다.
다만, 용액도포법에 의해 후처리 피막을 형성할 경우, 도포 후 건조시 건조 온도를 150℃ 미만으로 제어할 필요가 있다. 만약, 건조 온도가 150℃ 이상일 경우, 후처리 피막 형성용 조성물의 a/b 대비 후처리 피막의 a/b가 낮아져 실러 접착성 개선의 목적을 달성하기 어려울 수 있다.
본 발명에서는 후처리 피막의 피막 부착량에 대해 특별히 한정하지 않으나, 제한되지 않는 일 예에 따르면, 후처리 피막의 피막 부착량은 100mg/m2 내지 1000mg/m2일 수 있다. 만약, 피막 부착량이 100mg/m2 미만일 경우 소재 자체의 조도로 인해 후처리 피막이 불균일하게 형성될 우려가 있으며, 반면, 1000mg/m2을 초과할 경우 제조 비용이 상승하고, 건조가 불충분하게 이뤄질 우려가 있다.
이하, 본 발명의 다른 측면인 실러 접착성이 우수한 후처리 피막 형성용 조성물에 대하여 상세히 설명한다.
본 발명의 다른 측면인 후처리 피막 형성용 조성물은 B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하며, 전술한 바와 같이, 필요에 따라, Mn, Mo 및 W로부터 선택된 1종 이상의 B군 원소의 산화물 또는 산화물염을 포함할 수 있다. 후처리 피막이 상기와 같은 성분들을 포함하도록 하는 이유는 상술한 바와 같다. 한편, 본 발명에서는 상기 성분들 외 다른 유효한 성분의 첨가를 배제하는 것은 아니며, 예를 들어, 평활제 등을 추가로 포함할 수 있다.
한편, 본 발명의 피막 형성용 조성물은 하기의 성분들이 물과 같은 용매에 용해된 용액 형태로도 제공될 수 있으며, 단순히 하기의 성분들이 혼합된 분말 형태로도 제공될 수 있다. 만약, 본 발명의 피막 형성용 조성물이 용액 형태로 제공될 경우, 아래에서 설명하는 각 성분의 함량, 산소 원자의 함량, 산소 원자의 몰수비 등은 물과 같은 용매를 제외한 비휘발성 고형분만을 기준으로 하여 측정한 값에 해당한다.
본 발명의 피막 형성용 조성물은 산소 원자의 함량은 50원자% 이상인 것을 특징으로 한다. 피막 형성용 조성물 내 산소 원자의 함량을 상기와 같은 범위로 제어하는 이유는 상술한 바와 같다. 여기서, 피막 형성용 조성물 내 산소 원자의 함량은 피막 형성용 조성물을 이루는 구체적인 성분들의 분자 구조로부터 산출될 수 있다.
또한, 본 발명의 피막 형성용 조성물은 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 것을 특징으로 한다. a/b를 상기와 같은 범위로 제어하는 이유는 상술한 바와 같다. 여기서, a/b는 피막 형성용 조성물을 이루는 구체적인 성분들의 분자 구조로부터 산출될 수 있다.
본 발명에서는 피막 형성용 조성물의 pH에 대해서는 특별히 한정하지 않으나, 도금층 용해를 방지하면서도, 안정된 피막을 형성하기 위해서는 pH가 3.0 내지 7.0인 것이 바람직하다.
이하, 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나, 이러한 실시예의 기재는 본 발명의 실시를 예시하기 위한 것일 뿐 이러한 실시예의 기재에 의하여 본 발명이 제한되는 것은 아니다. 본 발명의 권리범위는 특허청구범위에 기재된 사항과 이로부터 합리적으로 유추되는 사항에 의하여 결정되는 것이기 때문이다.
(실시예)
두께 0.8mm, 연신율 36~37%, 도금량 35g/m2, 도금층이 Al 1.4%, Mg 1.4%, Zn 97.2%로 구성되는 아연계 도금강판을 준비하고, 아연계 도금강판 상에 후처리 코팅용액을 바코팅법으로 도포후 PMT 100℃ 조건에서 부착량이 300mg/m2이 되도록 후처리 피막을 형성하였다. 각 시편에 있어서, 피막 형성용 조성물을 이루는 성분들의 함량만을 달리하여 후처리 피막을 제작하였으며, 제작된 후처리 피막에 함유된 각 성분들의 함량을 하기 표 1에 나타내었다. 한편, 하기 표 1에서 종래예는 후처리 피막을 형성하지 아니한 예에 해당한다.
이후, 후처리 피막 내 산소 함량 및 a/b를 측정하였으며, 그 결과를 하기 표 1에 함께 나타내었다. 이때, 후처리 피막 내 산소 함량은 후처리 피막이 형성된 아연계 도금 강재를 XPS(X-ray Photoelectron Spectroscopy) 분석법으로 측정한 나노미터 스케일의 단위 깊이 별 평균값이며, a/b는 XPS 분석법을 이용하여 측정한 산소(O) Binding Energy Peak의 Curve Fitting을 통하여 구해진 단위 깊이 별 평균값이다.
이후, 각 시편의 가공성, 실러 접착성 및 탈막성을 평가하였으며, 그 결과를 하기 표 1에 함께 나타내었다.
<가공성 평가>
가공성을 평가하기 위해서 컵드로잉 시험을 실시하였으며, 상기 컵드로잉 시험은 금형과 펀치로 구성된 시험기를 사용하였으며, BHF(Blank Holding Force)를 높여가면서 시험을 진행하여 소재 파단이 일어나기 직전의 BHF값을 최대 BHF값으로 하여 표 1에 기재하였다. 최대 BHF값이 클수록 가공성이 우수함을 의미하며, 본 실시예에서 시행한 컵드로잉 시험의 상세 조건은 아래와 같다.
※ 컵드로잉 시험 상세조건
- 펀치 직경(Punch diameter): 50mm
- 펀치 끝단 반경(Punch edge radius): 6mm
- 금형 직경(Die diameter): 52.25mm
- 펀치 이동속도: 230mm/min
- 후처리 피막은 금형과 접촉하며, 표면에 세정유 도포 후 시험을 실시함
<실러 접착성 평가>
접착성 시험은 25mmX100mm 크기로 시편 2장을 제작하여, 세정유 도포 후 수직으로 세워 1일 방치한 다음, 시편 끝단으로부터 10mm 안쪽에 25mm(폭)X25mm(길이)X3mm(높이) 크기로 유향수 실러(mastic sealer) 접착제를 도포하고, 나머지 시편을 포개어 170℃에서 20분 동안 경화시킨 후, 상/하 시편의 접착 전단강도를 측정하였으며, 그 결과를 표 1에 나타내었다. 전단강도는 50mm/min의 속도로 측정하였으며, 측정된 최대 전단력을 접착면적 6.25cm2로 나누어 표기하였다. 이 때 실러 접착성 양호 여부는 접착강도 1.0 kgf/cm2를 기준으로, 이 값 이상이면 양호한 것으로 판단하였다.
<탈막성 평가>
탈막성 시험은 자동차 제조공정에서 사용되는 탈지용액을 사용하여 50~55℃에서 2분간 소재를 교반 침지하고 수세한 후, 소재 표면에 잔류하는 코팅피막의 양을 측정하여 탈지 전의 피막 부착량에 대한 탈막율을 백분율로 계산하여 표 1에 나타내었다. 코팅피막 잔류량은 일정 면적의 코팅층을 산 용액으로 용해 후 용해 용액의 몰리브덴 함량을 ICP(Inductively Coupled Plasma)로 정량 분석하여 면적당 잔류량을 계산하였다.
구 분 후처리 피막 조성 물성평가 결과
Mo산염화합물(wt%) 붕소화합물(wt%) PEG(wt%) 기타첨가제(wt%) 피막내산소함량(Atom%) a/b c/d 최대BHF(ton) 접착강도(kgf/cm2) 탈막율(%)
종래예 - - - - - - 6 0.4 -
비교예1 76.90 0.00 18.08 5.02 48.23 0.01 0.00 12 0.8 93
비교예2 70.41 6.12 18.37 5.10 51.84 0.17 0.28 11 0.9 96
발명예1 66.67 10.78 17.65 4.90 53.51 0.31 0.51 10 1.3 95
발명예2 49.77 20.93 22.93 6.37 54.54 0.68 1.33 11 2.1 93
발명예3 41.32 32.00 20.88 5.80 57.91 1.21 2.45 9 4.2 93
발명예4 39.77 34.09 20.45 5.68 58.52 1.33 2.72 13 4.5 94
발명예5 28.09 46.48 19.90 5.53 61.26 2.25 5.24 14 5.0 93
발명예6 20.10 57.01 17.91 4.98 63.79 3.46 8.99 10 5.0 95
발명예7 16.13 63.04 16.30 4.53 65.29 4.47 12.38 13 5.1 95
발명예8 13.45 65.36 16.58 4.61 65.57 4.98 15.40 10 5.2 96
발명예9 7.90 72.90 15.03 4.18 67.16 7.21 29.24 12 5.1 97
발명예10 2.63 77.19 15.79 4.39 67.54 9.37 92.94 11 4.8 97
발명예11 0.89 78.57 16.07 4.46 67.65 10.28 278.83 13 4.8 99
발명예12 0.00 80.23 15.48 4.30 68.05 11.46 - 11 4.3 98
표 1를 참조할 때, 산소(O) 함량이 50원자% 미만이거나 a/b가 0.3 미만인 비교예 1 및 2와 종래예의 경우 접착강도 1.0 kgf/cm2 미만으로 실러 접착성 기준을 만족하지 못한다는 것을 알 수 있다.
이와 달리, 후처리 피막내 산소(O) 함량이 50원자% 이상이고 a/b가 0.3 이상인 발명예 1 내지 12는 접착강도 기준 1.0 kgf/cm2 이상을 충분히 만족하며, 특히, 피막내 산소(O) 함량 및 a/b가 증가할수록 접착강도가 증가하는 경향을 보여준다. 다만, 발명예 11 및 12의 경우 코팅후 건조시 피막 조성이 균일하지 않아, 얼룩이 다소 발생하였다.
한편, 접착강도 기준이 1.0kgf/cm2이기는 하나, 전단강도 평가후 접착부 파단면의 응집파괴율 등을 고려하고, 보다 견고한 접착강도 확보를 위해서는, 상기 후처리 피막내 포함된 산소(O) 함량이 55원자% 이상이고, a/b가 1.0 이상인 것이 더욱 바람직하다고 할 것이다.
최대 BHF값 및 탈막성은 피막내 산소함량이나 a/b에 상관없이 모든 후처리 피막 조건에서 우수한 특성을 보이고 있다. 특히, 최대 BHF값은 후처리 피막이 형성된 비교예 1, 2 및 발명예 1 내지 12에서 모두 무처리재인 종래예 대비 높은 값을 나타내고 있으며, 이는 후처리 피막 형성시 가공성이 현저히 향상된다는 것을 의미한다.
한편, 본 실시예에서는 피막내 a/b를 다량의 산화물 또는 산화물염과 소량의 유기화합물로 제어하였으나, 여기에 국한되는 것은 아니며, 추가로 피막 내 30중량% 이하로 구성되는 유기 화합물의 분자 구조 내 존재하는 산소와 하이드록시기의 비율을 가지고도 제어할 수 있음은 물론이다.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.

Claims (18)

  1. 소지철과 상기 소지철 상에 순차로 형성된 아연계 도금층 및 후처리 피막을 포함하고, 상기 후처리 피막은 B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하고, 상기 후처리 피막 내 산소 원자의 함량은 50원자% 이상이며, 상기 후처리 피막 내 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 아연계 도금 강재.
  2. 제1항에 있어서,
    상기 후처리 피막은 Mn, Mo 및 W로부터 선택된 1종 이상의 B군 원소의 산화물 또는 산화물염을 더 포함하는 아연계 도금 강재.
  3. 제1항에 있어서,
    상기 후처리 피막 내 산소 원자의 함량은 55원자% 이상인 아연계 도금 강재.
  4. 제1항에 있어서,
    상기 후처리 피막 내 산소 원자의 함량은 60원자% 이상인 아연계 도금 강재.
  5. 제1항에 있어서,
    상기 a/b가 10.0 이하인 아연계 도금 강재.
  6. 제1항에 있어서,
    상기 a/b가 1.0 이상 9.0 이하인 아연계 도금 강재.
  7. 제1항에 있어서,
    상기 a/b가 2.0 이상 8.0 이하인 아연계 도금 강재.
  8. 제1항에 있어서,
    상기 A군 원소의 산화물 또는 산화물염은 pH 4~7 범위의 수용액에서 적어도 1개 이상의 수산기를 가지는 아연계 도금 강재.
  9. 제2항에 있어서,
    상기 A군 원소의 산화물 또는 산화물염은 pH 4~7 범위의 수용액에서 적어도 1개 이상의 수산기를 가지며, 상기 A군 원소의 몰수를 c라 하고, 상기 B군 원소의 몰수를 d라 할 때, c/d가 0.5 이상인 아연계 도금 강재.
  10. 제9항에 있어서,
    상기 c/d가 100 이하인 아연계 도금 강재.
  11. 제9항에 있어서,
    상기 c/d가 2.0 이상 50 이하인 아연계 도금 강재.
  12. 제9항에 있어서,
    상기 c/d가 5.0 이상 30 이하인 아연계 도금 강재.
  13. 제1항에 있어서,
    상기 후처리 피막 100중량부에 대하여 상기 유기 화합물은 5중량부 내지 30중량부로 포함되는 아연계 도금 강재.
  14. 제1항에 있어서,
    상기 유기 화합물은 적어도 1개 이상의 수산기 혹은 카르복시기를 가지는 아연계 도금 강재.
  15. 제1항에 있어서,
    상기 유기 화합물은 폴리비닐아세테이트(PVAc), 폴리비닐알콜(PVA), 폴리아크릴산(PAA), 폴리비닐부티랄(PVB) 및 폴리에틸렌글리콜(PEG)로부터 선택된 1종 이상인 아연계 도금 강재.
  16. 제1항에 있어서,
    상기 후처리 피막의 피막 부착량은 100mg/m2 내지 1000mg/m2인 아연계 도금 강재.
  17. B, Al, V 및 Fe로부터 선택된 1종 이상의 A군 원소의 산화물 또는 산화물염과 유기 화합물을 포함하고, 산소 원자의 함량은 50원자% 이상이며, 수소와 공유 결합을 이루는 산소 원자의 몰수를 a라 하고, 수소와 공유 결합을 이루지 않는 산소 원자의 몰수를 b라 할 때, a/b가 0.3 이상인 후처리 피막 형성용 조성물.
  18. 제17항에 있어서,
    상기 피막 형성용 조성물의 pH는 3.0 내지 7.0인 후처리 피막 형성용 조성물.
PCT/KR2017/015402 2016-12-23 2017-12-22 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물 WO2018117759A2 (ko)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2019533459A JP6850889B2 (ja) 2016-12-23 2017-12-22 シーラー接着性に優れた亜鉛系めっき鋼材及び後処理被膜形成用組成物
CN201780080160.3A CN110121570B (zh) 2016-12-23 2017-12-22 密封剂粘合性优异的镀锌系钢材及后处理薄膜形成用组合物
US16/471,889 US11299639B2 (en) 2016-12-23 2017-12-22 Zinc-based plated steel material having excellent sealer adhesion
EP17882913.1A EP3561145A4 (en) 2016-12-23 2017-12-22 ZINC PLATED STEEL MATERIAL WITH OUTSTANDING SEALANCE AND COMPOSITION FOR FORMING A POST-TREATMENT FILM

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0177331 2016-12-23
KR1020160177331A KR101940882B1 (ko) 2016-12-23 2016-12-23 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물

Publications (2)

Publication Number Publication Date
WO2018117759A2 true WO2018117759A2 (ko) 2018-06-28
WO2018117759A3 WO2018117759A3 (ko) 2018-08-23

Family

ID=62626860

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/015402 WO2018117759A2 (ko) 2016-12-23 2017-12-22 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물

Country Status (6)

Country Link
US (1) US11299639B2 (ko)
EP (1) EP3561145A4 (ko)
JP (1) JP6850889B2 (ko)
KR (1) KR101940882B1 (ko)
CN (1) CN110121570B (ko)
WO (1) WO2018117759A2 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101696115B1 (ko) * 2015-12-22 2017-01-13 주식회사 포스코 후처리 피막이 형성된 아연계 도금강판 및 그 후처리 방법
CN110835757B (zh) * 2019-10-22 2021-12-21 首钢集团有限公司 一种胶接性能优异的热镀锌钢板及其制备方法
KR102410808B1 (ko) 2020-09-08 2022-06-20 주식회사 포스코 아연도금강판의 표면개질 방법 및 그에 따라 표면개질된 아연도금강판
KR20220116698A (ko) 2021-02-15 2022-08-23 주식회사 엠.이.시 고분자 접착제와의 접착성이 우수한 Mg이 함유 용융아연도금강판의 제조방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010074527A (ko) 2000-01-24 2001-08-04 사또미 유따까 아연함유 도금강판의 인산염 화성처리 방법
JP2014185381A (ja) 2013-03-25 2014-10-02 Jfe Steel Corp 溶融亜鉛めっき鋼板およびその製造方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372148A (en) 1972-04-25 1974-10-30 Molins Ltd Conveyor systems for cigarettes and other similar rod-like articles
JPH05214559A (ja) 1992-02-06 1993-08-24 Kawasaki Steel Corp プレス成形性に優れたアルミニウム合金板
JP3445683B2 (ja) 1995-04-26 2003-09-08 新日本製鐵株式会社 プレス性、化成処理性、接着剤適合性に優れた亜鉛系めっき鋼板の製造方法
JP3132979B2 (ja) 1995-04-28 2001-02-05 新日本製鐵株式会社 潤滑性、化成処理性、接着剤適合性に優れた亜鉛系めっき鋼板
JPH09156031A (ja) * 1995-12-05 1997-06-17 Kawasaki Steel Corp プレス成形性、端面耐食性に優れた潤滑樹脂処理鋼板
JPH09268375A (ja) 1996-04-02 1997-10-14 Nippon Steel Corp 塗覆装鋼管の製造方法
JPH1018050A (ja) * 1996-06-28 1998-01-20 Nkk Corp 耐白錆性に優れる亜鉛系めっき鋼板
TWI221861B (en) * 1998-04-22 2004-10-11 Toyo Boseki Agent for treating metallic surface, surface-treated metal material and coated metal material
JP2000178761A (ja) 1998-12-14 2000-06-27 Kawasaki Steel Corp 亜鉛系めっき鋼板用表面処理剤及び表面処理亜鉛系めっき鋼板
KR100322063B1 (ko) * 1999-01-13 2002-03-12 김순택 도전막 형성용 조성물, 그 제조방법 및 그를 이용하여 제조된 도전막을 구비한 음극선관
JP3851482B2 (ja) 2000-02-18 2006-11-29 株式会社神戸製鋼所 耐白錆性および塗膜密着性に優れる亜鉛系めっき鋼板
CN100441728C (zh) 2003-04-18 2008-12-10 杰富意钢铁株式会社 冲压成形性优异的热镀锌钢板及其制造方法
JP4546884B2 (ja) 2004-07-07 2010-09-22 新日本製鐵株式会社 加工部耐食性に優れる表面処理めっき鋼板
MX2009002399A (es) 2006-09-07 2009-03-20 Nippon Steel Corp Liquido de tratamiento acuoso para lamina de acero recubierta con sn que tiene excelente resistencia a la corrosion y adhesion de recubrimiento y metodo para producir una lamina de acero con tratamiento superficial.
JP5012704B2 (ja) * 2008-07-08 2012-08-29 株式会社デンソー 車両用撮影システム
JP5338195B2 (ja) * 2008-08-20 2013-11-13 新日鐵住金株式会社 表面処理亜鉛系めっき鋼板及びその製造方法
JP5638191B2 (ja) * 2008-11-05 2014-12-10 日本パーカライジング株式会社 化成処理金属板およびその製造方法
KR101103669B1 (ko) * 2009-08-26 2012-01-11 주식회사 유니코정밀화학 강판 코팅용 조성물 및 강판
KR101253919B1 (ko) 2011-09-05 2013-04-16 주식회사 유니코정밀화학 용융아연도금강판의 피막 형성용 코팅용액 조성물 및 그 피막이 형성된 용융아연도금강판
KR101322063B1 (ko) * 2012-05-07 2013-10-28 주식회사 포스코 Ｍｏ계 혼합 조성물 및 이를 이용한 내흑화성과 전기전도성이 우수한 표면처리강판
JP5888268B2 (ja) * 2012-06-15 2016-03-16 Ｊｆｅスチール株式会社 高強度溶融亜鉛めっき鋼板の製造方法および高強度溶融亜鉛めっき鋼板
JP5588058B1 (ja) * 2013-03-29 2014-09-10 日本ペイント株式会社 クロムフリー金属表面処理剤
KR101696115B1 (ko) 2015-12-22 2017-01-13 주식회사 포스코 후처리 피막이 형성된 아연계 도금강판 및 그 후처리 방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010074527A (ko) 2000-01-24 2001-08-04 사또미 유따까 아연함유 도금강판의 인산염 화성처리 방법
JP2014185381A (ja) 2013-03-25 2014-10-02 Jfe Steel Corp 溶融亜鉛めっき鋼板およびその製造方法

Also Published As

Publication number Publication date
EP3561145A4 (en) 2019-12-11
CN110121570A (zh) 2019-08-13
WO2018117759A3 (ko) 2018-08-23
CN110121570B (zh) 2021-06-01
JP6850889B2 (ja) 2021-03-31
US11299639B2 (en) 2022-04-12
US20190315977A1 (en) 2019-10-17
JP2020514532A (ja) 2020-05-21
EP3561145A2 (en) 2019-10-30
KR101940882B1 (ko) 2019-01-21
KR20180073855A (ko) 2018-07-03

Similar Documents

Publication Publication Date Title
WO2018117759A2 (ko) 실러 접착성이 우수한 아연계 도금 강재 및 후처리 피막 형성용 조성물
WO2018230932A1 (ko) 강판 표면처리용 조성물, 이를 이용한 표면처리강판 및 이의 제조방법
US11255010B2 (en) Zinc-based plated steel sheet having post-treated coating formed thereon
US6537674B1 (en) Surface treated steel sheet
WO2018088876A1 (ko) 연료탱크 강판용 복합수지 조성물, 이를 이용한 복합수지코팅강판 및 그 제조방법
US3765955A (en) Surface treated steel sheet for use in a forming operation
KR101091341B1 (ko) 가공성, 접착성, 용접성 및 알카리 탈막성이 우수한 강판 코팅용 조성물 및 아연 또는 아연계 합금도금 강판
KR100782720B1 (ko) 합금화용융아연도금강판용 코팅 조성물, 이를 이용한피막형성방법 및 이에 따라 형성된 피막을 갖는 강판
JP3265973B2 (ja) プレス成形性に優れた亜鉛系めっき鋼板およびその製造方法
KR100916118B1 (ko) 아연 및 아연계 합금 도금강판용 코팅조성물, 이를 이용한피막형성방법 및 이에 따라 형성된 피막을 갖는 강판
KR20110111283A (ko) 단면 또는 양면 아연도금 강판으로 성형 부품을 제조하는 방법
KR100992316B1 (ko) 아연 및 아연계 합금 도금강판용 코팅조성물, 이를 이용한피막형성방법 및 이에 따라 형성된 피막을 갖는 강판
CN110546303A (zh) 用于处理金属表面的含水酸性组合物、使用这种组合物的处理方法和经处理的金属表面的用途
JP4100080B2 (ja) リチウムシリケート系潤滑処理鋼帯
JP2697579B2 (ja) 純亜鉛電気めっき鋼板
KR100920596B1 (ko) 가공성, 접착성 및 화성처리성이 우수한 아연 또는 아연계합금 도금강판 및 그 제조방법
JP3903904B2 (ja) 塗装性に優れた表面処理鋼板
JP3196635B2 (ja) 潤滑性ならびにプレス成形後の耐食性および外観に優れた溶融亜鉛めっき鋼板
CN116987996A (zh) 一种具有优良脱脂性能的锌镁铝镀层钢板及其制造方法
KR20160077532A (ko) 고강도 냉연강판의 피막형성용 코팅조성물 및 그 피막이 형성된 냉연강판
WO2024136360A1 (ko) 탈지성이 우수한 도금강판 및 이의 제조방법
KR100711446B1 (ko) 인산염처리성이 우수한 용융알루미늄도금 강판의 제조방법
KR101207765B1 (ko) 도금강판의 피막 형성용 코팅용액 조성물 및 그 피막이 형성된 강판
KR20240044561A (ko) 주석도금강판용 수성 표면처리제 조성물, 이를 포함하는 주석도금강판 및 주석도금 강판의 코팅방법
CN117165888A (zh) 一种具有优异脱脂和磷化性能的锌系镀层钢板及其制造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17882913

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2019533459

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017882913

Country of ref document: EP

Effective date: 20190723