EP1518944B1 - Verzinnte stahlplatte und herstellungsverfahren dafür - Google Patents

Verzinnte stahlplatte und herstellungsverfahren dafür Download PDF

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Publication number
EP1518944B1
EP1518944B1 EP03733259.0A EP03733259A EP1518944B1 EP 1518944 B1 EP1518944 B1 EP 1518944B1 EP 03733259 A EP03733259 A EP 03733259A EP 1518944 B1 EP1518944 B1 EP 1518944B1
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Prior art keywords
tin
steel sheet
chemical conversion
coating
plating layer
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English (en)
French (fr)
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EP1518944A4 (de
EP1518944A1 (de
Inventor
Hisatada I. P. D. Jfe Steel Corporation NAKAKOJI
Tomofumi I. P. D. Jfe Steel Corporation SHIGEKUNI
Takumi I. P. D. Jfe Steel Corporation TANAKA
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JFE Steel Corp
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JFE Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C2/08—Tin 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to tin-plated steel sheets and methods for producing the same. More particularly, the present invention relates to a tin-plated steel sheet which requires solderability and a method for producing the same.
  • Pb-Sn alloy solder has been used for bonding in household electric appliances, such as audio products and personal computers.
  • Pb in the alloy solder is harmful to the human body
  • use of Pb has been restricted and conversion to Pb-free solder has been in progress.
  • Pb-Sn alloy-plated steel sheets which are suitable for conventional Pb-Sn soldering have been used.
  • novel steel sheets having excellent Pb-free solderability without using Pb have been demanded.
  • the surfaces of the conventional Pb-Sn alloy-plated steel sheets are subjected to chromate treatment.
  • the consumer-electronics industry is moving toward prevention of the use of hazardous hexavalent chromium, and non-use of chromate treatment is required for newly produced steel sheets to be soldered.
  • Steel sheets to be subjected to Pb-free soldering are disclosed, for example, in Japanese Examined Patent Application Publications Nos. 6-99837 and 6-33466 , in which films mainly composed of Sn-Zn, Zn-Ni, Sn-Ni, and Fe-Ni are formed on a steel sheet, and a chromate film is further formed thereon.
  • Japanese Unexamined Patent Application Publication No. 2001-32085 discloses a surface-treated steel sheet in which a Cr-free post-treated film containing Si is formed on an Sn or Sn alloy-plating film.
  • a Cr-free post-treated film containing Si is formed on an Sn or Sn alloy-plating film.
  • an Fe-Sn alloy layer is not interposed between the steel sheet and the Sn-plating layer, adhesion between the steel sheet and the Sn-plating layer is poor, and Pb-free solderability is also unsatisfactory.
  • a surface treatment method for a tin-plated steel sheet is disclosed in Japanese Examined Patent Application Publication No. 55-24516 , in which a Cr-free chemical conversion coating is formed on a tin-plated steel sheet by DC electrolysis using the tin-plated steel sheet as a cathode in a phosphoric acid-based solution.
  • Japanese Examined Patent Application Publication No. 1-32308 also discloses a tin electroplated sheet used for seamless cans, in which a Cr-free chemical conversion coating in which P alone or P and Al are incorporated is formed on the surface of the tin-plated sheet.
  • the present invention provides a tin-plated steel sheet comprising a steel sheet having a surface roughness Ra of 1.5 ⁇ m or less, an Fe-Sn alloy layer disposed on a surface of the steel sheet, and a tin-plating layer disposed on the Fe-Sn alloy layer, the tin-plating layer having a coverage of more than 99% and a coating weight of 5 to 20 g/m 2 .
  • a chemical conversion coating containing P and Si is provided on the upper surface of the tin-plating layer. In the chemical conversion coating, the coating weight of P is 0.5 to 10 mg/m 2 and the coating weight of Si is 3 to 30 mg/m 2 .
  • the surface roughness Ra is preferably 1 ⁇ m or less.
  • the Fe-Sn alloy layer is preferably formed by tin melting treatment.
  • the chemical conversion coating is preferably formed with a chemical conversion treatment solution containing P and a silane coupling agent.
  • the silane coupling agent preferably contains an epoxy group.
  • the present invention provides a method for producing a tin-plated steel sheet, comprising the steps of (a) forming tin-containing plating layers on at least one surface of a steel sheet, (b) immersing the steel sheet provided with the plating layers in a chemical conversion treatment solution containing phosphate ions and a silane coupling agent or applying the chemical conversion treatment solution to the steel sheet, (c) heating the steel sheet to a temperature of 80°C to 200°C with the chemical conversion treatment solution being present on the plating layers to dry the steel, (d) washing the dried steel sheet with water, and (e) drying the water-washed steel sheet.
  • the chemical conversion treatment solution preferably contains a surfactant.
  • Pb-Sn alloy solder has a low melting point, for example, 37%Pb-Sn alloy solder has a melting point of 184°C.
  • Sn-3.5%Ag-0.75%Cu alloy solder which is predominantly used as Pb-free solder, has a high melting point at 219°C. Because of its high melting point, the Pb-free solder has lower soldering performance compared with the Pb-Sn alloy solder. Therefore, steel sheets to be soldered must have higher solderability.
  • Corrosion resistance and whisker resistance are also required for steel sheets to be soldered. Accordingly, the present inventors have conducted thorough research to overcome the problems described above based on tin plating mainly composed of Sn, which is the principal component of Pb-free solder. As a result, it has been found that all the properties described above can be satisfied when a tin-plating layer with a predetermined coating weight is formed on a steel sheet having a surface roughness Ra of 1.5 ⁇ m or less with an Fe-Sn alloy layer therebetween, the Fe-Sn alloy layer being formed by tin melting treatment, and a chemical conversion coating containing P and Si is formed on the tin-plating layer.
  • a chemical conversion coating containing proper amounts of P and Si on the tin-plating layer preferably using a chemical conversion treatment solution containing P and a silane coupling agent, excellent solderability with Pb-free solder can be exhibited.
  • the chemical conversion coating functions as an effective protective film to prevent degradation with time, excellent solderability with Pb-free solder is ensured even after an accelerated degradation test.
  • the chemical conversion coating provides excellent corrosion resistance and whisker resistance.
  • a tin-plated steel sheet of the present invention includes a steel sheet having a surface roughness Ra of 1.5 ⁇ m or less, an Fe-Sn alloy layer formed by tin melting treatment on a surface of the steel sheet, a tin-plating layer having a coverage of more than 99% on the Fe-Sn alloy layer, and a chemical conversion coating containing P and Si formed on the tin-plating layer using a chemical conversion treatment solution containing P and a silane coupling agent.
  • the coating weight of P is set in the range of 0.5 to 10 mg/m 2 and the coating weight of Si is set in the range of 3 to 30 mg/m 2 .
  • the ratio Si/P (by mass) in the chemical conversion coating is set in the range of 5 to 30.
  • the tin plating is melted by tin melting treatment (reflow treatment) so that an Fe-Sn alloy layer is formed as an intermediate layer at the interface with the steel sheet.
  • the coating weight of metallic Sn is preferably 5.0 to 20.0 g/m 2 after the formation of the Fe-Sn alloy layer.
  • the silane coupling agent contains an epoxy group.
  • a tin-plating layer is formed on the surface of a steel sheet having a surface roughness Ra of 1.5 ⁇ m or less with an Fe-Sn alloy layer therebetween, the Fe-Sn alloy layer being formed by tin melting treatment.
  • the tin-plating layer is formed so as to cover substantially the entire surface of the substrate, and more specifically, to have a coverage of more than 99%. If the ratio of covering the Fe-Sn alloy layer by the tin-plating layer, i.e., the coverage at the surface area, is 99% or less, satisfactory solderability cannot be achieved, and also corrosion resistance becomes insufficient.
  • tin melting treatment also referred to as "reflow treatment”
  • the tin layer as-electroplated stress of electrodeposits is present, and acicular crystals called whiskers grow from the surface of the tin layer due to energy that tries to liberate the stress of electrodeposits. Since whiskers cause short circuits in electric circuits, no whisker growth is required.
  • tin melting treatment is essential in the present invention.
  • the present inventors have newly found that, with respect to the coating weight of Sn in the present invention, if the surface roughness of the steel sheet is set at 1.5 ⁇ m or less in terms of centerline average (Ra), degradation of corrosion resistance in the convex portions is negligible. Therefore, the surface roughness Ra of the steel sheet is set at 1.5 ⁇ m or less.
  • the Fe-Sn alloy layer is formed at the interface between the steel sheet and the tin layer.
  • the Fe-Sn alloy layer is extremely important because it improves the adhesion between the steel sheet and the tin-plating layer, thus preventing the tin layer from peeling off during working, and also ensures solderability between the steel sheet and solder when the tin layer is melted in a solder bath during soldering. Consequently, in the present invention, interposition of the Fe-Sn alloy layer between the steel sheet and the tin layer is essential.
  • the amount of the Fe-Sn layer formed is preferably 0.05 g/m 2 in terms of the coating weight.
  • the alloy layer is harder than the tin-plating layer, the alloy layer degrades workability. Therefore, it is necessary to suppress the amount of the alloy layer formed, and the coating weight of the Fe-Sn alloy layer is preferably 1 g/m 2 or less and more preferably 0.7 g/m 2 or less.
  • Ni-based pretreatment such as Ni flash plating or Ni diffusion
  • the amount the alloy formed during the tin melting treatment is suppressed, and thus such Ni-based pretreatment may be used appropriately.
  • the coating weight of the tin-plating layer which is not alloyed after the tin melting treatment is preferably 5 to 20.0 g/m 2 . If the coating weight of the tin-plating layer is less than 5.0 g/m 2 , it is not possible to achieve satisfactory solderability with Pb-free solder and also corrosion resistance becomes insufficient. If the coating weight exceeds 20.0 g/m 2 , although satisfactory solderability and corrosion resistance are achieved, the cost is increased, which is undesirable. Additionally, the coating weight of Sn can be measured by coulometry or surface analysis using fluorescent X-rays.
  • the major feature of the present invention is that a chemical conversion coating containing P and Si is formed on the tin-plating layer, preferably by using a chemical conversion treatment solution containing P and a silane coupling agent, and the coating weights of P and Si in the chemical conversion coating are set in the ranges of 0.5 to 10.0 mg/m 2 and 3 to 30 mg/m 2 , respectively.
  • the coating weight of Si is preferably smaller. If the surface roughness Ra of the steel sheet, i.e., mother sheet to be plated, is decreased, the surface area of the steel sheet can be decreased and the Sn content can be increased. Consequently, even if the Si content is smaller, the Sn surface can be coated, and satisfactory solderability and corrosion resistance are ensured.
  • the present inventors have found that even if the coating weight of Si in the chemical conversion coating is less than 30 mg/m 2 , by setting the surface roughness Ra of the steel sheet, i.e., mother sheet to be plated, at 1.5 ⁇ m or less, satisfactory solderability and corrosion resistance can be obtained. Additionally, the surface roughness of the steel sheet can be adjusted, for example, by controlling the surface roughness in temper rolling.
  • the coating weight of Si in the chemical conversion coating when the coating weight of Si in the chemical conversion coating is small, the surface roughness of the mother sheet to be plated must be decreased. Even when the coating weight of Si in the chemical conversion coating is set at 3 to 30 mg/m 2 , in order to satisfy the characteristics, such as satisfactory solderability and corrosion resistance, the surface roughness Ra of the steel sheet, i.e., mother sheet to be plated, must be set at 1.5 ⁇ m or less. Even when the coating weight of Si in the chemical conversion coating is set at 30 mg/m 2 or less, as described above, the coating weight of the tin plating layer is set at 5 g/cm 2 or more. In view of stability in corrosion resistance, the coating weight of the tin plating layer is set at preferably 7.5 g/m 2 or more and more preferably 10 g/m 2 or more.
  • the coating weight of Si incorporated in the chemical conversion coating is less than 3 mg/m 2 , even if the surface roughness Ra of the steel sheet, i.e., mother sheet to be soldered, is 1.5 ⁇ m or less, coverage of the chemical conversion coating becomes insufficient and tin oxides grow on the Sn surface with time, resulting in a degradation in solderability and corrosion resistance. Therefore, the coating weight of Si must be set at 3 mg/m 2 or more. If the surface roughness Ra of the steel sheet, i.e., mother sheet to be plated, is 1.5 ⁇ m or less, even if the coating weight of Si incorporated in the chemical conversion coating exceeds 30 mg/m 2 , satisfactory solderability and corrosion resistance can be obtained. However, from the economical standpoint, the coating weight of Si incorporated in the chemical conversion coating is set at 30 mg/m 2 or less. Additionally, the coating weight of Si is measured by surface analysis using fluorescent X-rays.
  • Si is incorporated in the chemical conversion coating preferably by a silane coupling agent contained in the chemical conversion treatment solution.
  • the general chemical formula of the silane coupling agent is X-Si-OR 2or3 (OR: alkoxy group).
  • the alkoxysilyl group (Si-OR) of the silane coupling agent is hydrolyzed by water to form a silanol group, which is brought into close contact with the OH-group on the surface of the metal and forms a strong film by dehydrocondensation.
  • silane coupling agent examples include 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)3-aminopropyltrimethoxysilane, N-2-(aminoethyl)3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethoxysilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and amino group-containing compounds, such as N-2-(aminoethyl)3-aminopropyltrimethoxysilane
  • silane coupling agents with the general chemical formula X-Si-OR 2or3 wherein X contains an epoxy group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, are preferably used.
  • phosphoric acid-based conversion treatment is preferably used.
  • the P source for the chemical conversion treatment solution phosphoric acid, a metal salt, such as sodium phosphate, aluminum phosphate, or potassium phosphate, and/or a monohydrogen phosphate salt are more preferably used at a concentration of 1 to 80 g/l (in terms of phosphate ions).
  • a chemical conversion treatment solution containing the silane coupling agent described above is used. In such a case, by adjusting the pH of the chemical conversion treatment solution in the range of 1.5 to 5.5, it is possible to uniformly dissolve the silane coupling agent in the chemical conversion treatment solution.
  • a metal salt of Sn, Fe, or Ni such as SnCl 2 , FeCl 2 , NiCl 2 , SnSO 4 , FeSO 4 , or NiSO 4 , may be added to the chemical conversion treatment solution as appropriate.
  • an oxidizing agent such as sodium chlorate or a nitrite salt
  • an etching agent such as fluorine ions
  • a surfactant such as sodium lauryl sulfate or acetylene glycol, may also be appropriately added to the chemical conversion treatment solution.
  • melting (reflow) treatment is performed at a temperature not less than the melting point (231.9°C) of tin to form an intermediate layer composed of an Fe-Sn alloy and an upper metallic Sn layer, followed by conversion treatment by immersion. Additionally, in order to remove tin oxides generated on the surface after the reflow treatment, cathode treatment may be performed at 1 C/dm 2 in a 15 g/l sodium carbonate aqueous solution.
  • an aqueous solution containing 1 to 80 g/l (in terms of phosphate ions) phosphoric acid, 0.001 to 10 g/l (in terms of tin ions) stannous chloride, and 0.1 to 1.0 g/l sodium chlorate to which 0.5 to 20.0% by mass of a silane coupling agent is further added is used.
  • the temperature is set at 40°C to 80°C, and the treatment (immersion) time is set at 1 to 5 seconds.
  • the tin-plated steel sheet is dried at 80°C to 150°C and then washed with water, followed by drying by hot air.
  • Tin-plating layers were formed on both surfaces of cold-rolled steel sheets composed of a low carbon steel or ultra-low carbon steel with a thickness of 0.4 to 1.8 mm with Fe-Sn alloy layers therebetween, the coating weight of the tin-plating layer being 5.0 to 20.0 g/m 2 for each surface.
  • Chemical conversion coatings were formed under the conversion treatment conditions shown in Table 1 on the tin-plated steel sheets. The compositions of the chemical conversion coatings formed are shown in Table 2.
  • tin-plated steel sheets were produced.
  • at least one of the intermediate layer, tin-plating layer, and chemical conversion coating was out of the proper ranges of the present invention.
  • the surface roughness Ra of the cold-rolled steel sheet, i.e., mother sheet to be plated, used in each of Examples and Comparative Examples is a centerline average measured with a "Surfcom 500A" manufactured by Tokyo Seimitsu Co., Ltd.
  • the coating weight of Sn of the tin-plating layer and the coating weights of P and Si contained in the chemical conversion coating were measured using fluorescent X-rays.
  • the Sn coverage was measured by surface analysis using a scanning electron microscope (10 visual fields observed at a magnification of 5,000).
  • a Phosphoric acid 1-80 g/L Immersion Silane coupling agent (a) 0.5-20 mass% Stannous chloride 0.001-10 g/L Sodium chlorate 0.1-1.0 g/L B Phosphoric acid 1-80 g/L Immersion Silane coupling agent (b) 0.5-20 mass% Ferrous chloride 0.001-10 g/L Sodium chlorate 0.1-1.0 g/L C Phosphoric acid 1-80 g/L Roll coating Silane coupling agent (c) 0.5-20 mass% Nickel chloride 0.001-10 g/L Sodium chlorate 0.1-1.0 g/L
  • solder As Pb-free solder, Sn-3.5%Ag-0.75%Cu solder manufactured by Senju Metal Industry Co., Ltd. was used. The solder temperature was set at 245°C, and using a "SAT-5100" system manufactured by Rhesca Co., Ltd. and by a wetting balance method, zero-crossing time at which the sheet became solderable was measured to evaluate the solderability. A sample with a sheet thickness of 0.6 mm was used for the evaluation after it was subjected to accelerated degradation by being exposed to a chamber at a temperature of 105°C, a relative humidity of 100%, and a pressure of 1.22 ⁇ 10 5 Pa for 8 hours. The sample was dipped in a solder bath at a dipping rate of 3 mm/sec and a dipping depth of 3 mm. A zero-crossing time of 3 seconds or less was evaluated to be acceptable.
  • a three-cycle corrosion test was carried out, in which each cycle consisted of 8 hours of salt spraying (according to JIS Z 2371) and 16 hours of spray halt, and corrosion resistance was evaluated based on the red rusting area rate (%).
  • a sample was bent at a bend radius of 5 mm and was subjected to a 500-thermal cycle test in which -25°C and 120°C were repeated.
  • the surface of the bent section was observed with a scanning electron microscope to check the generation of whiskers. Whisker resistance was evaluated based on the generation and length of whiskers.
  • the present inventors have conducted thorough research on a method for stably forming a chemical conversion coating containing P and Si on a tin-based plating layer, and in particular, a production method in which an Si coating weight of 3 mg/m 2 or more can be obtained stably.
  • a chemical conversion coating can be stably formed in a short period of time by a method including the steps of immersing a tin-based plated steel sheet in a chemical conversion treatment solution containing phosphate ions and a silane coupling agent or applying the chemical conversion treatment solution to the steel sheet, heat-drying the steel sheet at 80°C to 200°C with the chemical conversion treatment solution being present on the plating layer, washing the dried steel sheet with water, and drying the water-washed steel sheet.
  • the film of the chemical conversion treatment solution on the steel sheet becomes more uniform during heat drying, and thus a stable chemical conversion coating can be obtained, which is preferable.
  • a "tin-based plated steel sheet” means a steel sheet provided with a plating layer containing tin on one or both surfaces.
  • the plating layer containing tin include, but are not limited to, an alloy layer containing Sn and at least one metal selected from the group consisting of Ni, Fe, Zn, Bi, and Cu; and a two-layered plating film including a metallic tin layer and an intermediate layer formed between the metallic tin layer and the steel sheet, the intermediate layer being composed of a tin alloy containing at least one metal selected from the group consisting of Fe and Ni.
  • the intermediate layer may be a two-layered film including an Fe-Ni alloy layer and an Fe-Sn-Ni alloy layer formed on the upper surface of the Fe-Ni alloy layer.
  • the ratio Ni/(Fe + Ni) (by mass) is preferably 0.02 to 0.50. If the ratio Ni/(Fe + Ni) (by mass) is less than 0.02, an alloy layer mainly composed of an Fe-Sn alloy with tetragonal crystals is formed, and thereby the amount of interstices increases, resulting in a decrease in corrosion resistance. It also becomes difficult to continuously form the silane film, resulting in a small improvement in paint adhesion.
  • an undercoat may be applied by nickel plating or the like between the steel sheet and the plating layer containing tin.
  • the chemical conversion coating containing P and Si is preferably formed, for example, by phosphoric acid-based conversion treatment.
  • phosphoric acid a metal salt, such as sodium phosphate, aluminum phosphate, or potassium phosphate, and/or a monohydrogen phosphate salt are more preferably used at a concentration of 1 to 80 g/l (in terms of phosphate ions).
  • the reason for setting the preferred concentration in terms of phosphate ions in the chemical conversion treatment solution to be in the range of 1 to 80 g/l is as follows. If the concentration is less than 1 g/l, paint adhesion and corrosion resistance are degraded. On the other hand, if the concentration exceeds 80 g/l, defects easily occur in the chemical conversion coating, resulting in a degradation in paint adhesion and corrosion resistance. In addition, there may be a case in which unreacted phosphoric acid remains, resulting in a degradation in paint adhesion.
  • a silane coupling agent As the Si source for the chemical conversion treatment solution, a silane coupling agent is used.
  • the general chemical formula of the silane coupling agent is X-Si-OR 2or3 (OR: alkoxy group).
  • the alkoxysilyl group (Si-OR) is hydrolyzed by water to form a silanol group, which is brought into close contact with the OH-group on the surface of the metal by dehydrocondensation.
  • the pH of the chemical conversion treatment solution is preferably in the range of 1.5 to 5.5. That is, by adjusting the pH of the chemical conversion treatment solution in the range of 1.5 to 5.5, it is possible to uniformly dissolve the silane coupling agent in the chemical conversion treatment solution.
  • silane coupling agent examples include 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)3-aminopropyltrimethoxysilane, N-2-(aminoethyl)3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethoxysilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and amino group-containing compounds, such as N-2-(aminoethyl)3-aminopropyltrimethoxysilane
  • silane coupling agents with the general chemical formula X-Si-OR 2or3 wherein X contains an epoxy group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, are preferably used.
  • a metal salt of Sn, Fe, or Ni such as SnCl 2 , FeCl 2 , NiCl 2 , SnSO 4 , FeSO 4 , or NiSO 4 , may be added to the chemical conversion treatment solution as appropriate.
  • an oxidizing agent such as sodium chlorate or a nitrite salt
  • an etching agent such as fluorine ions
  • a surfactant such as sodium lauryl sulfate or acetylene glycol, is appropriately added to the chemical conversion treatment solution.
  • the tin-based plated steel sheet is immersed in the chemical conversion treatment solution at 40°C to 80°C for 1 to 5 seconds and is then drawn with a roller or the like so that the chemical conversion treatment solution forms a film with a proper thickness.
  • the steel sheet provided with the chemical conversion treatment solution is dried by heating at 80°C to 200°C.
  • dehydrocondensation is accelerated between the silanol group resulting from the hydrolysis of the alkoxysilyl group (Si-OR) and the OH group on the surface of the metal, and thereby the chemical conversion coating is formed stably. It is difficult to obtain a Si coating weight of 5 mg/m 2 or more in the film only by immersion treatment because of slow dehydrocondensation reaction.
  • Heating must be performed with the chemical conversion treatment solution being present on the steel sheet. Therefore, a hot air blowing method which is usually industrially used is not suitable. Preferably, infrared heating, induction heating, or radiation heating is performed.
  • the steel sheet temperature must be 80°C to 200°C. If the temperature is less than 80°C, the dehydrocondensation rate is decreased and the formation of the chemical conversion coating becomes unstable. Consequently, it is not possible to obtain a sufficient Si amount. If the temperature exceeds 200°C, although the dehydrocondensation proceeds quickly enough, tin is oxidized on the surface of the tin-based plating layer, and also heating energy is consumed excessively, which is not desirable.
  • a method may be employed in which the chemical conversion treatment solution is applied to the steel sheet using a roll coater that makes it easy to control the thickness of the film of the solution on the steel sheet.
  • melting (reflow) treatment is performed at a temperature not less than the melting point (231.9°C) of tin to form a tin-based plating layer including an Fe-Sn alloy layer (intermediate layer) and a metallic Sn layer (upper layer), followed by conversion treatment by immersion.
  • cathode treatment may be performed at 1 C/dm 2 in a 15 g/l sodium carbonate aqueous solution.
  • an aqueous solution containing 1 to 80 g/l (in terms of phosphate ions) phosphoric acid, 0.001 to 10 g/l (in terms of tin ions) stannous chloride, and 0.1 to 1.0 g/l sodium chlorate to which 0.5 to 20.0% by mass of a silane coupling agent is further added is used.
  • the temperature is set at 40°C to 80°C, and the treatment (immersion) time is set at 1 to 5 seconds.
  • the tin-plated steel sheet which has been subjected to conversion treatment is drawn with a ringer roll so that the film of the chemical conversion treatment solution has a predetermined thickness.
  • the steel sheet is then heat dried at 110°C with an infrared heater. Immediately after drying, the steel sheet is water-washed, followed by drying with hot air at 35°C to 90°C.
  • Tin-based plating layers having the compositions shown in Table 3 were formed on both surfaces of cold-rolled steel sheets composed of a low carbon steel or ultra-low carbon steel with a thickness of 0.1 to 2.0 mm, the coating weight of the tin-based plating layer being 10 g/m 2 for each surface.
  • Each steel sheet was immersed in a chemical conversion treatment solution selected from the three chemical conversion treatment solutions A to C shown in Table 1 or subjected to roll coating using the chemical conversion treatment solution. Immediately after heat drying, water washing was performed, followed by hot air drying. Chemical conversion coatings were thereby formed.
  • the heating method and heating temperature in the heat-drying step for forming the chemical conversion coatings are also shown in Table 3.

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

Claims (6)

  1. Verzinntes Stahlblech, das umfasst:
    einen Stahl,
    eine Fe-Sn-Legierungsschicht, die auf einer Oberfläche des Stahlblechs ausgebildet ist,
    eine Zinn-Plattierungsschicht, die auf der Fe-Sn-Legierungsschicht ausgebildet ist, wobei die Zinn-Plattierungsschicht eine Deckung von mehr als 99% aufweist, und
    eine chemische Konversionsbeschichtung, die P und Si enthält und auf der Zinn-Plattierungsschicht vorgesehen ist, wobei die chemische Konversionsbeschichtung ein Beschichtungsgewicht von P: 0,5 bis 10 mg/m2 und ein Beschichtungsgewicht von Si: 3 bis 30 mg/m2 aufweist,
    wobei
    die Zinn-Plattierungsschicht ein Beschichtungsgewicht von 7,5 g/m2 bis 20 g/m2 aufweist und das Stahlblech eine Oberflächenrauheit Ra von 1,5 µm oder weniger aufweist.
  2. Verzinntes Stahlblech nach Anspruch 1, wobei die Fe-Sn-Legierungsschicht ein Beschichtungsgewicht von 1 g/m2 oder weniger aufweist.
  3. Verzinntes Stahlblech nach Anspruch 1, wobei die chemische Konversionsbeschichtung ein Verhältnis Si/P (nach Masse) von 5 bis 30 aufweist.
  4. Verfahren zum Herstellen eines verzinnten Stahlblechs mit einer chemischen Konversionsbeschichtung, die ein Beschichtungsgewicht von P: 0,5 bis 10 mg/m2 und ein Beschichtungsgewicht von Si: 3 bis 30 mg/m2 aufweist, wobei das Verfahren die folgenden Schritte umfasst:
    Ausbilden einer Zinn enthaltenden Plattierungsschicht mit einem Beschichtungsgewicht von 7,5 g/m2 bis 20 g/m2 auf wenigstens einer Oberfläche des Stahlblechs durch das Durchführen einer Schmelzbehandlung bei einer Temperatur von nicht weniger als dem Schmelzpunkt von Zinn,
    Eintauchen des Stahlblechs mit der daran vorgesehen Plattierungsschicht in eine chemische Konversionsbehandlungslösung, die Phosphationen und ein Silan-Haftmittel enthält,
    oder Auftragen einer chemischen Konversionsbehandlungslösung, die Phosphationen und
    ein Silan-Haftmittel enthält, auf das Stahlblech,
    Erhitzen des Stahlblechs mit der chemischen Konversionsbehandlungslösung auf der Plattierungsschicht zu einer Temperatur von 80°C bis 200°C, um das Stahlblech zu trocknen,
    Spülen des getrockneten Stahlblechs mit Wasser, und
    Trocknen des wassergespülten Stahlblechs.
  5. Verfahren zum Herstellen eines verzinnten Stahlblechs nach Anspruch 4, wobei die chemische Konversionsbehandlungslösung ein Oberflächenbehandlungsmittel enthält.
  6. Verfahren zum Herstellen eines verzinnten Stahlblechs nach Anspruch 4, wobei das Silan-Haftmittel eine Epoxy-Gruppe enthält.
EP03733259.0A 2002-06-05 2003-06-03 Verzinnte stahlplatte und herstellungsverfahren dafür Expired - Lifetime EP1518944B1 (de)

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US20070007144A1 (en) * 2005-07-11 2007-01-11 Schetty Robert A Iii Tin electrodeposits having properties or characteristics that minimize tin whisker growth
JP2009046754A (ja) * 2007-08-23 2009-03-05 Toyo Seikan Kaisha Ltd 溶接缶用表面処理錫めっき鋼板及びこれから成る溶接缶
JP5633117B2 (ja) * 2008-05-12 2014-12-03 Ｊｆｅスチール株式会社 錫めっき鋼板の製造方法および錫めっき鋼板ならびに化成処理液
JP5338163B2 (ja) * 2008-07-10 2013-11-13 Ｊｆｅスチール株式会社 錫めっき鋼板の製造方法
WO2011045833A1 (ja) * 2009-10-14 2011-04-21 東洋鋼鈑株式会社 樹脂被覆金属板の製造方法
DE102011000984A1 (de) * 2011-03-01 2012-09-06 Rasselstein Gmbh Verfahren zum Veredeln einer metallischen Beschichtung auf einem Stahlband
CN102828225B (zh) * 2011-06-16 2015-06-17 宝山钢铁股份有限公司 一种用于电镀铬的阳极板及其制造工艺
WO2017204265A1 (ja) * 2016-05-24 2017-11-30 新日鐵住金株式会社 Ｓｎめっき鋼板
US10865491B2 (en) * 2016-05-24 2020-12-15 Nippon Steel Corporation Sn-based alloy plated steel sheet
US11598009B2 (en) 2018-03-01 2023-03-07 Nippon Steel Corporation Sn-plated steel sheet and method for manufacturing Sn-plated steel sheet
CN114855230B (zh) * 2022-04-15 2024-10-18 首钢集团有限公司 一种高附着力镀锡板及其制备方法
CN117070932A (zh) * 2023-08-11 2023-11-17 马鞍山钢铁股份有限公司 一种具有优异前处理性能的冷轧连续退火钢板及其制造方法
CN118213334B (zh) * 2024-05-21 2024-09-17 华羿微电子股份有限公司 一种功率器件及降低功率器件焊接空洞的预处理方法

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