WO2023090458A1 - 表面処理鋼材 - Google Patents

表面処理鋼材 Download PDF

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Publication number
WO2023090458A1
WO2023090458A1 PCT/JP2022/043202 JP2022043202W WO2023090458A1 WO 2023090458 A1 WO2023090458 A1 WO 2023090458A1 JP 2022043202 W JP2022043202 W JP 2022043202W WO 2023090458 A1 WO2023090458 A1 WO 2023090458A1
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WIPO (PCT)
Prior art keywords
chemical conversion
steel material
corrosion resistance
siloxane bond
absorbance
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/043202
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English (en)
French (fr)
Japanese (ja)
Inventor
義勝 西田
厚雄 清水
晋 上野
浩雅 莊司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=86396980&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2023090458(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to EP22895739.5A priority Critical patent/EP4438769A4/en
Priority to AU2022393009A priority patent/AU2022393009B2/en
Priority to MX2024005896A priority patent/MX2024005896A/es
Priority to JP2023562438A priority patent/JP7445185B2/ja
Priority to CA3236461A priority patent/CA3236461C/en
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to US18/708,525 priority patent/US12559830B2/en
Priority to KR1020247015780A priority patent/KR20240089649A/ko
Priority to CN202280074627.4A priority patent/CN118234892A/zh
Publication of WO2023090458A1 publication Critical patent/WO2023090458A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/52—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions more than one element being applied in one step
    • 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
    • B32B15/08—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
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • 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
    • 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
    • C23C22/34—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • 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
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    • Y10T428/00—Stock material or miscellaneous articles
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    • 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
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    • 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
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a surface-treated steel material. This application claims priority based on Japanese Patent Application No. 2021-189292 filed in Japan on November 22, 2021, the contents of which are incorporated herein.
  • plated steel sheets in which a coating layer mainly composed of zinc is formed on the surface of steel sheets have been used in a wide range of applications such as automobiles, building materials, and home appliances.
  • a method of treating with a metal surface treatment agent that does not contain chromium, a method of applying a phosphate treatment, a method of applying a treatment with a silane coupling agent alone, a method of applying an organic resin film treatment, etc. are generally known. and is put to practical use.
  • Patent Document 1 describes an organosilicon compound (W) obtained by blending two kinds of silane coupling agents having a specific structure on the surface of a metal material at a specific mass ratio.
  • W organosilicon compound
  • a chromate-free surface-treated metal material is disclosed in which a composite coating containing each component is formed by coating and drying a water-based metal surface treatment agent containing a specific inhibitor.
  • Patent Document 2 discloses a surface-treated metal material subjected to a chromate-free surface treatment that is excellent in each element of corrosion resistance, heat resistance, fingerprint resistance, conductivity, paintability, and black residue resistance during processing, and a metal A chromium-free metal surface treatment is disclosed for use in imparting superior corrosion and alkali resistance to materials.
  • Patent Document 3 discloses a chromate-free precoated metal plate in which an upper coating film ( ⁇ ) is formed on at least one side of the metal plate, wherein the metal plate and the upper coating film ( ⁇ ) , (1) a silane coupling agent (A) containing an amino group in the molecule and a silane coupling agent (B) containing a glycidyl group in the molecule are blended and reacted to obtain a cyclic siloxane in the structure It has a bond and a chain siloxane bond, and the abundance ratio of the cyclic siloxane bond and the chain siloxane bond indicates the cyclic siloxane bond by the FT- IR reflection method.
  • a silane coupling agent (A) containing an amino group in the molecule and a silane coupling agent (B) containing a glycidyl group in the molecule are blended and reacted to obtain a cyclic siloxane in the structure It has a bond and a chain silox
  • a plate is disclosed.
  • Patent Document 1 and Patent Document 2 are surface-treated steel sheets that have been subjected to chromate-free surface treatment with excellent corrosion resistance, heat resistance, fingerprint resistance, electrical conductivity, paintability, and black residue resistance during processing. It is an excellent technology that has been put into practical use.
  • the corrosion resistance of the plating especially the initial white rust resistance
  • the corrosion resistance of the plating is not sufficient in the prior art for practical use. That is, in the techniques described in Patent Document 1 and Patent Document 2, when the test time in the SST test (salt spray test) that has been generally evaluated so far is exceeded, the corrosion resistance is higher than the flat portion (flat portion). There is concern that white rust may occur on the plated layer in the processed portion where the corrosion resistance is poor.
  • Patent Document 3 it is necessary to contain an organic resin as a film-forming component. Therefore, even if the corrosion resistance and coating film adhesion are excellent, there is a problem that the electrical conductivity is inferior.
  • the present invention provides a surface-treated steel material having excellent corrosion resistance and electrical conductivity, based on the premise of a surface-treated steel material having a chemical conversion coating on the surface of a zinc-based plated steel material having a plating layer containing zinc or a zinc alloy on the surface of the steel material.
  • the challenge is to
  • the corrosion resistance of the surface-treated steel having a chemical conversion coating is improved as the barrier property of the chemical conversion coating (property to prevent permeation of corrosion factors such as moisture and chloride ions) is higher.
  • substances (mainly metal elements) in the chemical conversion coating are leached out when moisture adheres, and the effect of preventing corrosion of the plating layer (inhibitor effect) is exhibited.
  • Corrosion resistance improves, so that it is high.
  • the chemical conversion coatings disclosed in Patent Documents 1 and 2 are coatings that have both barrier properties and inhibitory effects, but in an environment that requires higher corrosion resistance than in the past, the plating layer is Corrosion is a concern.
  • the present inventors have investigated a method for enhancing the barrier property and inhibitor effect of a chemical conversion coating, on the premise of a chemical conversion coating that does not necessarily contain an organic resin in order to obtain excellent conductivity. gone.
  • the chemical conversion treatment film contains an organosilicon compound as a film-forming component and P and F as inhibitor components, and the ratio of the alkylene group and the siloxane bond in the organosilicon compound is controlled.
  • the barrier property of the chemical conversion film was improved and the corrosion resistance was improved.
  • the inhibitor effect is improved and the corrosion resistance is further improved by controlling the ratio of the phosphate group and the siloxane bond in the chemical conversion coating. .
  • a surface-treated steel material comprises a steel material, a plating layer containing Zn or a Zn alloy formed on the surface of the steel material, a chemical conversion coating formed on the surface of the plating layer, and the chemical conversion treatment film contains an organosilicon compound having a siloxane bond, P and F, and the abundance ratio of the alkylene group and the siloxane bond in the organosilicon compound is determined by FT-IR When measured, A1/A2, which is the ratio of the absorbance peak value A1 at 2800 to 3000 cm ⁇ 1 indicating the alkylene group to the absorbance peak value A2 at 1030 to 1200 cm ⁇ 1 indicating the siloxane bond, is 0.10.
  • the siloxane A3/A2 which is the ratio of the absorbance A3 at 1200 cm ⁇ 1 of the phosphate group to the peak value A2 of the absorbance at 1030 to 1200 cm ⁇ 1 indicating binding, may be 0.43 to 1.00. .
  • FIG. 4 is a diagram showing the analysis results of FT-IR by the ATR method
  • FIG. 4 is a diagram showing the analysis results of FT-IR by the ATR method
  • the surface-treated steel material 1 according to the present embodiment includes a steel material 11, a plating layer 12 containing Zn or a Zn alloy formed on the surface of the steel material 11, and a and a chemical conversion coating 13 .
  • the plating layer 12 and the chemical conversion coating 13 are formed only on one side of the steel material 11 in FIG. 1, they may be formed on both sides.
  • the chemical conversion coating 13 contains an organosilicon compound having a siloxane bond, P and F, and the presence of an alkylene group and a siloxane bond in the organosilicon compound
  • A1/A2 is the ratio of the peak absorbance value A1 at 2800 to 3000 cm ⁇ 1 indicating the alkylene group to the peak value A2 at 1030 to 1200 cm ⁇ 1 indicating the siloxane bond. is between 0.10 and 0.75.
  • the siloxane bond is A3/A2, which is the ratio of the absorbance A3 of the phosphate group at 1200 cm ⁇ 1 to the peak value A2 of the absorbance at 1030 to 1200 cm ⁇ 1 , is 0.43 to 1.00.
  • the steel material 11, the plating layer 12, and the film 13 will be described below.
  • the surface-treated steel material 1 according to this embodiment has excellent corrosion resistance due to the plating layer 12 and the coating 13 . Therefore, the steel material 11 is not particularly limited.
  • the steel material 11 may be determined according to the product to be applied, the required strength, the thickness, etc., and is, for example, a hot-rolled steel sheet described in JIS G 3193: 2019, JIS G 3131: 2018, JIS G 3113: 2018, etc. , JIS G 3141:2021, JIS G 3135:2018, etc., can be used.
  • the chemical composition of the plating layer 12 is not limited as long as it is a plating layer containing 40% by mass or more of Zn or a Zn alloy (zinc-based plating layer).
  • plating specified in JIS G 3313:2021, JIS G 3302:2019, JIS G 3323:2019, JIS G 3317:2019, or JIS G 3321:2019 can be applied.
  • the adhesion amount of the plating layer 12 is not limited, it is preferably 10 g/m 2 or more per side in order to improve corrosion resistance. On the other hand, even if the coating amount per side exceeds 200 g/m 2 , the corrosion resistance is saturated and it is economically disadvantageous. Therefore, the adhesion amount is preferably 200 g/m 2 or less.
  • the type of plating layer is not limited.
  • it may be a hot dip plated layer or an electroplated layer.
  • the chemical conversion coating 13 provided on the surface-treated steel material 1 according to the present embodiment is formed by applying a treatment liquid (chemical conversion treatment liquid) containing a silane coupling agent, a phosphoric acid compound, and a fluorine compound on a plating layer containing zinc or a zinc alloy. can be obtained by coating the surface under predetermined conditions and drying it. Therefore, the chemical conversion coating 13 included in the surface-treated steel material 1 according to the present embodiment contains siloxane bonds (Si—O—Si bonds: cyclic siloxane bonds and chain siloxane bonds derived from silane coupling agents as film-forming components.
  • the chemical conversion coating 13 may contain Zr or V derived from a Zr compound or a V compound.
  • the chemical conversion film 13 included in the surface-treated steel material 1 according to this embodiment does not substantially contain an organic resin.
  • Whether or not the chemical conversion coating contains P and F is determined by a method of confirming the presence or absence of P and F in the surface-treated steel material using a fluorescent X-ray analyzer. Similar analysis can be performed when other elements such as Zr and V are included. If the detected intensity of each element is three times or more than that measured on a plated steel material without a film, it is determined that the element is contained in the film. Whether or not the chemical conversion film contains an organosilicon compound having a siloxane bond can be determined by FT-IR, which will be described later.
  • the absorbance peak value A2 at 1030 to 1200 cm ⁇ 1 indicating siloxane bonds, and 2800 to 3000 cm indicating alkylene groups A1/A2, which is the ratio of the absorbance peak value A1 of ⁇ 1 is 0.10 to 0.75
  • the chemical conversion coating contains an organosilicon compound having a siloxane bond as a film forming component and P (phosphoric acid compound) and F (fluorine compound) as inhibitor components, the alkylene group in the organosilicon compound and the siloxane bond
  • P (phosphoric acid compound) and F (fluorine compound) as inhibitor components
  • A1/A2 is from 0.10 to 0.75, the barrier property of the chemical conversion film is improved and the corrosion resistance is improved.
  • A1/A2 is more than 0.75 that is, when the proportion of alkylene groups in the organosilicon compound is large, organic matter remains in the SiOx skeleton, and corrosive factors such as moisture and chloride ions pass through the organic matter. becomes easier to permeate, resulting in lower corrosion resistance.
  • A1/A2 is preferably 0.60 or less, more preferably 0.55 or less, still more preferably 0.50 or less. On the other hand, when A1/A2 is less than 0.10, that is, when the proportion of siloxane bonds is high, cracks occur in the chemical conversion coating, resulting in deterioration of corrosion resistance. A1/A2 is preferably 0.15 or more, more preferably 0.20 or more.
  • the absorbance peak value A2 at 1030 to 1200 cm -1 indicating the siloxane bond , A3/A2, which is the ratio of the absorbance A3 at 1200 cm ⁇ 1 of the phosphate group, is 0.43 to 1.00
  • the chemical conversion coating 13 of the surface-treated steel material 1 according to the present embodiment which is mainly composed of a SiOx skeleton having a cyclic siloxane bond or a chain siloxane bond, and has P such as a phosphoric acid compound and F such as a fluorine compound as inhibitor components.
  • the inhibitor effect is improved by controlling the proportions of the phosphoric acid groups in the chemical conversion coating and the siloxane bonds in the organosilicon compound.
  • A3/A2 which is the ratio of the absorbance A3 at 1200 cm ⁇ 1 of the phosphate group to the peak value A2 of the absorbance at 1030 to 1200 cm ⁇ 1 indicating the siloxane bond.
  • A3/A2 is more preferably 0.45 or more, still more preferably 0.50 or more.
  • A3/A2 exceeds 1.00, the barrier property of the coating is lowered and the corrosion resistance is lowered.
  • A3/A2 is more preferably 0.80 or less, still more preferably 0.60 or less.
  • a general FT-IR device is used to measure the absorbance of specific peaks in the range corresponding to each of the alkylene group, siloxane bond, and phosphate group as described above, and A1, A2, After obtaining A3, it can be obtained by taking the ratio. Specifically, at the time of measurement, the absorbance at wavenumbers of 800 to 4000 cm ⁇ 1 is measured, and calculation is made from each absorbance value. The baseline correction for determining the absorbance is performed so that the absorbance at 4000 cm -1 , 2400 cm -1 , 2100 cm -1 and 850 cm -1 among the wavenumbers of 800 to 4000 cm -1 is zero.
  • measurement conditions are, for example, as follows. Measurement method: diffuse reflection method or ATR method Resolution: 4 cm -1 Accumulated times: 128 measurements Atmosphere: Atmosphere
  • the amount of chemical conversion coating 13 attached is preferably 100 to 2000 mg/m 2 . If the adhesion amount is less than 100 mg/m 2 , sufficient effects may not be obtained. On the other hand, if the coating amount is more than 2000 mg/m 2 , the coating may become too thick and peel off.
  • the surface-treated steel material according to the present embodiment can obtain the above effects regardless of the manufacturing method, but the following manufacturing method is preferable because it can be stably manufactured.
  • the surface-treated steel material according to this embodiment can be manufactured by a manufacturing method including the following steps.
  • a plating step of forming a plating layer containing Zn or a Zn alloy on the surface of a steel material such as a steel plate;
  • an application step of applying a chemical conversion treatment solution to a steel material having a plating layer;
  • a drying-cooling step of heating and drying the steel material to which the chemical conversion treatment liquid has been applied, followed by air cooling to form a chemical conversion coating. Preferred conditions are described for each step.
  • a steel material such as a steel sheet is immersed in a plating bath containing Zn or a Zn alloy, or electroplated to form a plating layer on the surface. Formation of the plated layer is not particularly limited. A normal method may be used so as to obtain sufficient plating adhesion. Further, the steel sheet to be subjected to the plating process and the manufacturing method thereof are not limited. As steel sheets to be immersed in the plating bath, for example, hot-rolled steel sheets described in JIS G 3193: 2019 and JIS G 3113: 2018 and cold-rolled steel sheets described in JIS G 3141: 2021 and JIS G 3135: 2018 are used. can be done. The composition of the plating bath may be adjusted according to the chemical composition of the desired plating layer. After pulling up the steel material from the plating bath, the amount of the plating layer deposited can be adjusted by wiping as necessary.
  • a steel material having a plating layer containing Zn or a Zn alloy is coated with a chemical conversion treatment liquid (surface treatment metal agent) containing a silane coupling agent, a phosphoric acid compound, and a fluorine compound.
  • a chemical conversion treatment liquid surface treatment metal agent
  • the coating method of the surface treatment metal agent is not limited. For example, it can be applied using a roll coater, bar coater, spray, or the like.
  • a silane coupling agent is included as a film-forming component.
  • a silane coupling agent (X) containing one amino group in the molecule and a silane coupling agent (Y) containing one glycidyl group in the molecule are mixed at a solid concentration ratio of A Si compound obtained by blending (X)/(Y) at 0.5 to 1.7 may be used.
  • Fluorine compounds contained in the chemical conversion treatment solution include hydrofluoric acid HF, hydroborofluoric acid BF 4 H, hydrosilicofluoric acid H 2 SiF 6 , zircon hydrofluoric acid H 2 ZrF 6 , and titanium hydrofluoric acid H 2 TiF.
  • Compounds such as 6 can be exemplified.
  • the compound may be one type or a combination of two or more types. Among these, hydrofluoric acid is more preferable. When hydrofluoric acid is used, better corrosion resistance and paintability can be obtained.
  • the phosphate compound contained in the chemical conversion solution remains as P as an inhibitor component in the chemical conversion film.
  • P as an inhibitor component improves the corrosion resistance of the chemical conversion coating.
  • the phosphoric acid compound contained in the chemical conversion treatment solution is not particularly limited, but examples include phosphoric acid, ammonium phosphate, potassium phosphate, and sodium phosphate. Among these, phosphoric acid is more preferable. Better corrosion resistance can be obtained when phosphoric acid is used.
  • the chemical conversion treatment liquid contains a Zr compound, zirconium ammonium carbonate, zirconium hexafluoride hydrochloride, zirconium hexafluoride ammonium and the like can be exemplified.
  • an organic compound having at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group and a phosphonic acid group can be used to form a pentavalent vanadium compound. may be reduced to tetravalent to divalent.
  • FIG. 2 is a diagram showing the results of FT-IR analysis by the ATR method, showing that CH2 in FIG. 2 is an alkylene group and SiO is a siloxane bond.
  • FIG 3 is an enlarged view of the wavenumber range of 1100 to 1250 cm ⁇ 1 in FIG.
  • the absorbance peak value A2 at 1030 to 1200 cm ⁇ 1 indicating siloxane bonds does not change significantly, while the absorbance peak at 2800 to 3000 cm ⁇ 1 indicating alkylene groups.
  • PMT is set to 155 to 200°C.
  • the heating method is not limited. For example, it can be dried by heating using an IH, a hot air oven, or the like.
  • the average heating rate is preferably 4 to 40° C./sec from the viewpoint of productivity.
  • air is blown onto the surface-treated steel material to cool it to room temperature (air-cooling).
  • A1/A2 can be efficiently reduced by blowing air onto the steel material having latent heat in the cooling process after drying (after reaching the PMT). It is more preferable that the air to be blown at that time is also blown to the steel material through the punching metal like the hot air in the drying process. If water cooling is performed after drying, the amount of heat for forming the SiOx skeleton cannot be obtained, and the alkylene compound remains in the coating. As a result, the abundance of alkylene groups increases, and the target corrosion resistance (initial white rust resistance) cannot be obtained.
  • the inhibitor component is eluted into the water-cooled water by water-cooling. Therefore, when controlling A3/A2, it is preferable to control the content of the phosphoric acid compound and to suppress the elution of the inhibitor component by air cooling after drying. Moreover, when controlling A3/A2, it is preferable to set the PMT to 160° C. or higher and air-cool the cooling after drying.
  • Plated steel sheets (metal sheet Nos. 1 to 8) having plating having the plating layer composition shown in Table 1 were prepared.
  • the adhesion amount of the plating layer was 70 g/m 2 .
  • Metal plate no. 1 is electroplating; 2 to 8 were produced by hot dip plating.
  • Zn-0.2% Al indicates a composition containing 0.2% by mass of Al, the balance being Zn and impurities, and Zn-6% Al-3% Mg , 6 mass % Al, 3 mass % Mg, the balance being Zn and impurities, and so on.
  • a cold-rolled steel sheet satisfying JIS G 3141:2021 was used as the base material of the plated steel sheet.
  • the coating of the chemical conversion treatment liquid was performed using a roll coater. After applying the chemical conversion treatment liquid, hot air is blown onto the steel plate through a punching metal (steel plate with multiple through holes), and the steel plate is heated to the dry plate temperature (PMT) in Table 2A at a heating rate of 4 to 10 ° C./sec. and then cooled to 20° C. by air cooling by blowing air through a punching metal or by water cooling. As a result, No. 1 to 21 surface-treated steel materials were obtained. In addition, hot air was blown onto the steel plate without using a punching metal to heat the steel plate to the dry plate temperature in Table 2A at a heating rate of 8 ° C./sec. , No. 22 and 23 surface-treated steel materials were obtained.
  • silane coupling agent (A) containing one amino group 3-aminopropyltrimethoxysilane (A1)
  • silane coupling agent (B) containing one glycidyl group in the molecule 3 -Glycidoxypropyltrimethoxysilane compounding ratio (A) / (B) is 0.5 as a solid content mass ratio, and the other composition is the same as the above, by adding a polyurethane resin to the treatment liquid.
  • No. 2 has a coating containing polyurethane resin in a weight that is 0.25 times the coating weight of No. 2; 24 surface-treated steels were obtained.
  • the chemical conversion film contained an organosilicon compound having a siloxane bond, and P and F.
  • ⁇ Flat portion corrosion resistance I> A salt spray test conforming to JIS Z 2371:2015 was performed on the flat plate test piece for up to 190 hours, and the corrosion resistance was evaluated based on the occurrence of white rust (area ratio) on the test piece after the test. Corrosion resistance evaluation criteria are shown below. It was determined that S and AA had sufficient corrosion resistance. (Evaluation criteria for corrosion resistance) S: 1% or less AA: more than 1%, 3% or less A: more than 3%, 5% or less B: more than 5%, 10% or less C: more than 10%
  • No. 1 which is an example of the present invention.
  • the chemical conversion film contained an organosilicon compound having a siloxane bond, a phosphoric acid compound and a fluorine compound, and A1/A2 was 0.10 to 0.75.
  • A1/A2 was 0.10 to 0.75.

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PCT/JP2022/043202 2021-11-22 2022-11-22 表面処理鋼材 Ceased WO2023090458A1 (ja)

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CA3236461A CA3236461C (en) 2021-11-22 2022-11-22 Surface-treated steel
EP22895739.5A EP4438769A4 (en) 2021-11-22 2022-11-22 SURFACE-TREATED STEEL MATERIAL
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