WO2001018275A1 - Ornement et son procede de preparation - Google Patents

Ornement et son procede de preparation Download PDF

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Publication number
WO2001018275A1
WO2001018275A1 PCT/JP2000/006086 JP0006086W WO0118275A1 WO 2001018275 A1 WO2001018275 A1 WO 2001018275A1 JP 0006086 W JP0006086 W JP 0006086W WO 0118275 A1 WO0118275 A1 WO 0118275A1
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WO
WIPO (PCT)
Prior art keywords
layer
stainless steel
watch exterior
band
watch
Prior art date
Application number
PCT/JP2000/006086
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Hachirou Kushida
Kenji Hanai
Yoshitugu Andou
Takeshi Inoue
Kazumi Hamano
Yukio Tanokura
Akira Meguro
Shinji Ikeda
Original Assignee
Citizen Watch Co., Ltd.
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
Priority claimed from JP25290099A external-priority patent/JP4350225B2/ja
Priority claimed from JP31943799A external-priority patent/JP4463353B2/ja
Priority claimed from JP2000104454A external-priority patent/JP4451536B2/ja
Application filed by Citizen Watch Co., Ltd. filed Critical Citizen Watch Co., Ltd.
Priority to EP00956994A priority Critical patent/EP1146136B1/en
Priority to US09/831,327 priority patent/US6905758B1/en
Publication of WO2001018275A1 publication Critical patent/WO2001018275A1/ja
Priority to HK02101696.3A priority patent/HK1040421B/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C8/06—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 gases
    • C23C8/08—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 gases only one element being applied
    • C23C8/20—Carburising
    • C23C8/22—Carburising of ferrous surfaces
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/005—Coating layers for jewellery
    • A44C27/006—Metallic coatings
    • 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
    • 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
    • C23C28/341—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 carbide 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
    • 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
    • C23C28/347—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 layers adapted for cutting tools or wear applications
    • 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
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/06—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 gases
    • C23C8/34—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 gases more than one element being applied in more than one step
    • 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
    • C23C8/80—After-treatment
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects

Definitions

  • the present invention relates to a decorative article (including a part) and a method for producing the same, and more specifically, a hardened layer in which solid solution atoms are dissolved at an arbitrary depth from a surface, for example, a carburized layer is formed.
  • Decorative articles such as watch exterior parts having a base material and their manufacturing methods, carburized stainless steel watch exterior parts, especially gas-carburized austenitic stainless steel watch bands, bezels, casings, back lids
  • the present invention relates to a watch exterior part such as a dial and a method for manufacturing the same, and a watch exterior part having a smooth surface or a mirror surface without so-called "yuzu skin” and a method for manufacturing the same. Background technology
  • Stainless steel, titanium, or titanium alloys are used for decorative items such as watch bands, bezels, cases, case backs, clasps, and dials.
  • austenitic stainless steel which has excellent corrosion resistance and decorativeness, is frequently used as stainless steel.
  • cold forging is performed on a plate made of SUS316 or SUS304, which is austenitic stainless steel.
  • SUS316 or SUS304 which is austenitic stainless steel.
  • Japanese Patent Application Laid-Open No. 54-86441 does not describe austenitic stainless steel, but uses gears, screws, and shafts made of low-carbon steel, low-alloy case-hardened steel, etc. It is stated that solid carburizing treatment of precision microparts such as can be performed at a temperature of 900 and the surface of the part can be barrel-polished to easily obtain a mirror surface.
  • chromium carbide precipitates on the surface of the stainless steel.
  • the chromium content of the stainless steel itself is reduced, and the corrosion resistance of the stainless steel is significantly reduced.
  • the chromium carbide is coarsened, there is a problem that high hardness cannot be obtained in the carburized region of the stainless steel.
  • a method of carburizing the stainless steel at a low temperature of less than 700 can be considered, but a carburizing treatment at such a low temperature results in a passivation film that impedes the penetration of carbon atoms to the surface of the stainless steel. Therefore, the surface of stainless steel cannot be hardened.
  • the austenitic stainless steel is subjected to gas carburizing at a low temperature of 400 to 500 in a carburizing gas atmosphere, followed by pickling or mechanical polishing (for example, soft blast, barrel polishing, puff polishing). Etc.).
  • the decorative article thus obtained for example, a wristwatch band, has a hard cured layer at a depth of 5 to 50 / m from the austenitic stainless steel surface of the base material while maintaining corrosion resistance, that is, A carburized layer is formed. Therefore, the surface of the base material presents a beautiful mirror surface, and the surface hardness of the mirror surface is Vickers hardness (HV) of 500 to 700, which is high, which cannot be obtained with stainless steel that has not been subjected to surface hardening treatment. It has hardness.
  • HV Vickers hardness
  • Decorative items including jewelry whose austenitic stainless steel surface is hardened in this way are hard to be scratched and have long-lasting beauty. There is an advantage that can be maintained.
  • decorative items such as wristwatch exterior parts and bracelets are required to have the same decorative value as other decorative items. For this reason, decorative surfaces are often formed on the surface of such accessories.
  • a gold alloy film formed by a wet plating method is widely used as such a decorative film.
  • JP-A-9-171854, JP-A-9-268634 and JP-A-9-324564 discloses austenitic technology. Precipitation and coarsening of chromium carbide in stainless steel do not occur because of the low-temperature carburizing of stainless steel. Layer F e and C coexist in stainless steel, possibly containing an oxide of iron such as F e 2 ⁇ 3 "mill scale" is formed on the outermost surface of the carburized layer. In the techniques described in these publications, black scale is removed by pickling treatment or mechanical polishing.
  • the pickling treatment alone cannot make the surface of the watch exterior part a mirror surface.
  • iron contained in the scale is melted by a strong acid solution, and the scale is peeled from the surface of the watch exterior component.
  • the stainless steel itself also contains iron, the strong acid solution will attack the surface of the carburized layer. As a result, the surface of the carburized layer after pickling is roughened and does not become mirror-finished.
  • the finish required on the surface of stainless steel watch exterior parts is not limited to mirror finish.
  • Various to get decorative aesthetics Mechanical finishing is required. For example, finishing such as a hair line that carves a number of parallel streaks and a honing that carves a number of fine recesses is required.
  • stainless steel watch exterior parts with excellent scratch resistance, a mirror-like surface, and austenitic stainless steel without impairing the excellent corrosion resistance inherent in stainless steel such as austenitic stainless steel.
  • Watch exterior parts such as pieces, which have been carburized at a low temperature, such as 400 to 500, as described above, have a beautiful mirror surface that is necessary for the watch exterior, despite being polished. It does not mean that it is observed as “yuzu skin” with fine irregularities.
  • Such “yuzu skin” is not limited to stainless steel, but is common when metal used for watch exteriors such as titanium and titanium alloy is subjected to surface hardening treatment, for example, carburizing, at a temperature lower than the recrystallization temperature of the metal. It is a phenomenon that occurs. Specifically, it is a phenomenon that occurs when surface hardening is performed at a temperature slightly higher than the recrystallization temperature.
  • such “yuzu skin” is not limited to carburizing treatment using carbon as a solid solution atom, but also occurs when nitrogen or oxygen is used as a solid solution atom and a surface hardening treatment is performed at a temperature less than a recrystallization temperature of a used metal. This is a common phenomenon.
  • An object of the present invention is to solve the problems associated with the prior art described above, and a conventional decoration is provided on a surface of a substrate on which a hardened layer, for example, a carburized layer is formed at an arbitrary depth from the surface.
  • An object of the present invention is to provide a decorative article having a higher surface hardness than that of a watch, that is, a decorative article having excellent scratch resistance, particularly a watch exterior part.
  • Another object of the present invention is to provide a base material having the cured layer formed thereon.
  • An object of the present invention is to provide a decorative article, particularly a watch exterior part, in which various colors such as gold are imparted to the surface of the decorative article without lowering the surface hardness, that is, without impairing the scratch resistance.
  • Another object of the present invention is to provide a method for producing the decorative article as described above.
  • Another object of the present invention is to provide a stainless steel watch exterior part having excellent scratch resistance and a mirror-finished surface without impairing the excellent corrosion resistance inherent to stainless steel such as austenitic stainless steel.
  • stainless steel, such as austenitic stainless steel which have excellent scratch resistance without impairing the excellent corrosion resistance inherent in stainless steel such as austenitic stainless steel, and whose surface has been subjected to mechanical finishing such as hairline processing and honing processing. It is an object of the present invention to provide a watch exterior part made of a product and a method for producing the same.
  • Another object of the present invention is to provide a metal used for a watch exterior, which has a smooth surface or a mirror surface without “yuzu skin” even when the surface is hardened at a temperature lower than the recrystallization temperature of the metal.
  • Another object of the present invention is to provide a watch exterior part having an excellent appearance and a method for manufacturing the same. Disclosure of the invention
  • a decorative article having a substrate on which a hardened layer in which solid solution atoms are dissolved at an arbitrary depth from the surface is formed
  • the solid solution atom is usually at least one atom selected from the group consisting of a carbon atom, a nitrogen atom and an oxygen atom.
  • the base material is preferably made of stainless steel, titanium or a titanium alloy.
  • the hard coating may be a coating exhibiting a color tone different from the color tone of the substrate surface.
  • the surface hardness of the hard coating is greater than the surface hardness of the substrate.
  • the hard coating is desirably made of a nitride, carbide, oxide, nitrocarbide, or nitrocarboxylate of an element in Groups 4a, 5a, and 6a of the periodic table.
  • a carbon hard coating is preferable.
  • An intermediate layer may be formed between the carbon hard coating and the surface of the cured layer of the substrate.
  • the intermediate layer includes a lower layer made of T i or Cr formed on the surface of the cured layer of the base material, and an upper layer made of Si or Ge formed on the surface of the lower layer. Intermediate layers are preferred.
  • At least two types of hard coatings may be formed on the surface of the hardened layer of the base material, and at least two types of hard coatings may be formed on the hardened layer of the base material. It may be laminated on the surface.
  • the hard coating may be formed on a part of the surface of the cured layer of the base material.
  • a gold alloy coating may be further formed on the hard coating.
  • gold alloy coating Al, Si, V, Cr, Ti, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Hf,
  • a coating made of an alloy of at least one metal selected from Ta, W, Ir and Pt is preferable.
  • Examples of the decorative article include watch exterior parts.
  • the method for producing a decorative article according to the present invention includes:
  • a hard coating is formed on the surface of a stainless steel substrate on which a hardened layer in which solid solution atoms are dissolved at an arbitrary depth from the surface is formed.
  • the decorative article obtained by the method for manufacturing a decorative article according to the present invention includes the decorative article according to the present invention, for example, a watch exterior part such as a wristwatch band.
  • the watch exterior part according to the present invention is
  • a watch exterior part made of stainless steel and having a carburized layer formed by dissolving carbon on the surface thereof that is, a watch exterior part made of stainless steel and having a carburized layer formed on the surface.
  • a polished surface having a Vickers hardness (HV) of 500 or more is formed on the surface of the carburized layer.
  • the polished surface has a mirror surface.
  • the watch exterior part according to the present invention includes:
  • a mechanically finished surface is formed on the surface of the carburized layer.
  • the Vickers hardness (H V) of the mechanically finished surface is preferably 500 or more.
  • the above-mentioned timepiece exterior component is obtained by forming a mechanical finish on the surface of the timepiece exterior component, and then performing a carburizing treatment.
  • a wristwatch band including a plurality of stainless steel pieces interconnected to each other,
  • a carburized layer in which carbon is dissolved as a solid is formed on the surface of the piece
  • a polished surface having a Vickers hardness (HV) of 500 or more is formed on the surface of the carburized layer.
  • the polished surface has a mirror surface.
  • a wristwatch band including a plurality of stainless steel pieces interconnected to each other,
  • a carburized layer in which carbon is dissolved as a solid is formed on the surface of the piece
  • a mechanically finished surface is formed on the surface of the carburized layer.
  • These wristwatch bands include a connecting part made of stainless steel for connecting the pieces to each other, and a carburized layer in which carbon is dissolved may be formed on at least a part of the surface of the connecting part. .
  • the wristwatch band according to the present invention is preferably a wristwatch band obtained by connecting a piece and a piece to each other with a connecting part, subjecting the piece and the connecting part to carburizing treatment, and then polishing the surface of the piece.
  • the wristwatch band according to the present invention may further include a connection component having no carburized layer.
  • the method for manufacturing a watch band according to the present invention includes:
  • the pieces and the connecting parts are fluorinated at 400 to 500 in a fluorine-based gas atmosphere.
  • the surface of the piece is barrel-polished.
  • mechanical finishing is performed on the surface of the pieces connected by the connecting component, whereby an arm watch band having a mechanically finished surface can be obtained.
  • a plurality of stainless steel pieces and a plurality of stainless steel connecting parts are fluorinated at 250 to 600 in a fluorine-based gas atmosphere
  • a gas carburizing treatment is performed at 400 to 500 in a carburizing gas atmosphere containing carbon monoxide
  • a wristwatch band having a mechanically finished surface by subjecting the surfaces of the plurality of pieces to mechanical finishing before the fluorination treatment Can be obtained.
  • the method for manufacturing a watch exterior part other than a watch band according to the present invention is a method for manufacturing a stainless steel watch exterior part other than a watch band in which a plurality of stainless steel pieces are connected by a plurality of stainless steel connecting parts.
  • the base material is fluorinated in a fluorine-based gas atmosphere at 250 to 60,
  • a gas carburizing treatment is performed at 400 to 500 in a carburizing gas atmosphere containing carbon monoxide
  • the surface of the base material is barrel-polished.
  • a watch exterior part having a mechanically finished surface can be obtained.
  • a watch band prepared by the method for manufacturing a watch band according to the present invention as described above is preferable.
  • the watch exterior component other than the watch band according to the present invention the watch exterior component other than the watch band prepared by the method for manufacturing the watch exterior component other than the watch band according to the present invention as described above is preferable. No.
  • austenitic stainless steel is preferable.
  • Other watch exterior parts according to the present invention Watch exterior parts made of metal,
  • a deformed layer including a fiber structure in which metal crystal grains are deformed into a fibrous form is formed on the metal surface, and at least a hardened layer in which solid solution atoms are dissolved in the deformed layer is formed.
  • the deformation layer is formed by applying a physical external force to at least the surface of the metal.
  • the deformation layer is preferably formed by applying a physical external force that extends the surface of the metal in substantially one direction.
  • the deformation layer is formed over a depth of 2 to 10 from the surface of the metal.
  • the hardened layer is formed to a depth of 5 to 50 m from the surface of the deformation layer.
  • the solid solution atom is at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, and an oxygen atom.
  • the surface hardness of the mirror surface of the cured layer is not less than 500 in Vickers hardness (HV).
  • a method for manufacturing a watch exterior part made of stainless steel wherein a physical external force is applied to the surface of the stainless steel, and at least the surface of the stainless steel includes a fibrous structure in which metal crystal grains are deformed into a fibrous form. Forming a deformation layer,
  • a hardening treatment is performed on the surface of the deformed layer to cause solid solution atoms to form a solid solution to form a hardened layer.
  • the deformation layer is formed on the surface of the stainless steel, It is preferable to form by applying a physical external force extending in the direction of the arrow.
  • the deformed layer is formed by applying at least one of a polishing process and a grinding process to the surface of the stainless steel, which applies a physical external force that extends the surface of the stainless steel in almost one direction.
  • the deformed layer is formed by polishing the surface of the shape, or
  • the surface having the desired shape may be a surface that is processed to be substantially flat, or may be a curved surface.
  • the deformation layer is preferably formed over a depth of 2 to 100 jum from the surface of the stainless steel.
  • the hardened layer is formed over a depth of 5 to 5 O m from the surface of the deformable layer.
  • the solid solution atom is at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, and an oxygen atom.
  • the mirror surface of the cured layer preferably has a surface hardness of Vickers hardness (HV) of 500 or more.
  • the deformed layer is usually formed on a stainless steel surface of a base material for a watch exterior part formed by forging with a large amount of deformation.
  • the hardening treatment is usually performed at a temperature below the recrystallization temperature of stainless steel.
  • the curing treatment may be performed at a temperature higher than the recrystallization temperature. However, under this temperature condition, it is not necessary to form the deformed layer because citron skin does not occur.
  • austenitic stainless steel is preferable.
  • the “watch exterior parts” in this specification include a watch band, a bezel, a casing, a back cover, a clasp, a dial, and the like.
  • FIG. 1 is a schematic diagram showing a structure of a band piece in Embodiment A1 of the present invention.
  • FIG. 2 is a schematic diagram showing a structure of a band piece in Embodiment A2 of the present invention.
  • FIG. 3 is a schematic diagram showing a structure of a band piece in Embodiment A3 of the present invention.
  • FIG. 4 is a schematic diagram showing a structure of a band piece in Embodiment A3 of the present invention.
  • FIG. 5 is a schematic view showing a surface treatment step of a band piece in Embodiment A4 of the present invention.
  • FIG. 6 is a schematic view showing a surface treatment step of a band piece in Embodiment A4 of the present invention.
  • FIG. 1 is a schematic diagram showing a structure of a band piece in Embodiment A1 of the present invention.
  • FIG. 2 is a schematic diagram showing a structure of a band piece in Embodiment A2 of the present invention.
  • FIG. 7 is a schematic diagram showing the structure of a band piece in Example A4 of the present invention.
  • FIG. 8 is a schematic diagram showing a structure of a band piece in Embodiment A5 of the present invention.
  • FIG. 9 is a schematic diagram showing a surface treatment step of a band piece in Embodiment A6 of the present invention.
  • FIG. 10 is a schematic diagram showing a structure of a band piece in Embodiment A6 of the present invention.
  • FIG. 11 is a schematic diagram showing a surface treatment step of a band piece in Example A7 of the present invention.
  • FIG. 12 shows Example A7 of the present invention. It is a schematic diagram which shows the surface treatment process of the piece of the band which cuts.
  • FIG. 13 is a schematic diagram showing a structure of a band piece in Embodiment A7 of the present invention.
  • FIG. 14 is a schematic diagram showing a surface treatment step of a band piece in Example A8 of the present invention.
  • FIG. 15 is a schematic diagram showing a surface treatment step of a band piece in Example A8 of the present invention.
  • FIG. 16 is a schematic diagram showing a structure of a band piece in Embodiment A8 of the present invention.
  • the decorative article according to the present invention comprises a base material on which a hardened layer in which solid solution atoms are dissolved, a hard coating formed on the surface of the hardened layer, and a hard coating formed on the hard coating if necessary. And a gold alloy film formed thereon.
  • decorative article base material used in the present invention include stainless steel, titanium metal, and titanium alloy.
  • Austenitic stainless steel is particularly preferably used as the stainless steel.
  • titanium metal means a metal material mainly composed of pure titanium, and refers to titanium type 1, titanium type 2, titanium type 3, etc. defined in the JIS standard.
  • a titanium alloy means a metal material obtained by adding aluminum, vanadium, iron, etc. to a metal mainly composed of pure titanium, and is a titanium 60 class and a titanium 60 E defined in the JIS standard. Refers to species. This In addition, various titanium alloys and various titanium-based intermetallic compounds are included in the titanium alloy material.
  • a hardened layer is formed by dissolving solid solution atoms on the surface of a substrate made of a metal or an alloy as described above.
  • the solid solution atom at least one kind of atom selected from the group consisting of a carbon atom, a nitrogen atom and an oxygen atom is used.
  • a carbon atom is dissolved in stainless steel, for example, austenitic stainless steel.
  • nitrogen and oxygen atoms are dissolved in stainless steel.
  • Nitrogen atoms and oxygen atoms may be dissolved in titanium or a titanium alloy. Further, carbon atoms may be dissolved in titanium or a titanium alloy.
  • the cured layer is preferably formed over a depth of 5 to 50 m from the surface of the substrate.
  • the surface hardness of the mirror surface of the cured layer is preferably Vickers hardness (HV; load of 50 g) of 500 or more.
  • a carburized layer is formed as a hardened layer on a substrate made of austenitic stainless steel not containing titanium metal, for example, the following steps are preferably performed.
  • the substrate Prior to forming the carburized layer, it is preferable to subject the substrate to a fluorination treatment at 100 to 500, preferably 150 to 300, in a fluorine-based gas atmosphere.
  • This austenitic stainless steel is, for example, Fe—Cr—N i-Mo stainless steel, Fe_Cr—Mn stainless steel.
  • a stable stainless steel having a small Ni content is desirable.
  • stainless steel having a high Ni content and containing about 1.5 to 4% by weight of Mo, which is a valuable element is desirable.
  • the most suitable austenitic stainless steel has a chromium content of 15 to 25% by weight, and is a stable stainless steel with an austenite phase stable even at room temperature. 4% by weight is added.
  • fluorine-based gas used in the above-mentioned fluorination treatment include NF 3 , CF 4 , SF 4 , C 2 F 6, BF 3 , CHF 3 , HF, SF 6 , WF 6, Si Fluorine compound gases such as F 4 and C 1 F 3 are mentioned. These fluorine compound gases can be used alone or in combination of two or more. In addition to these gases, other fluorine compound gases containing fluorine in the molecule can also be used as the fluorine-based gas. Furthermore, it is possible to use such a fluorine compound gas as a pyrolyzed was F 2 gas was generated or previously adjusted Ltd. was F 2 gas is also the fluorine-based gas, a thermal cracker. Such a fluorine compound gas and the F 2 gas are arbitrarily mixed and used.
  • the fluorine-based gas such as the above-mentioned fluorine compound gas and F 2 gas can be used alone, but usually they are used after being diluted with an inert gas such as nitrogen gas or argon gas.
  • concentration of the fluorinated gas itself in such a diluted gas is usually 10,000,000 to 10,000,000. 0,000 capacity p pm, preferably 20,000 to 70,000 capacity ppm, more preferably 30,000 to 500,000 capacity ⁇ ⁇ m .
  • a fluorine-based gas used in the present invention is the NF 3.
  • NF 3 is gaseous at room temperature, has high chemical stability, and is easy to handle. This NF 3 gas is usually used in combination with nitrogen gas within the above concentration range.
  • the fluoridation treatment in the present invention is performed, for example, at a temperature of 100 to 500 under a fluorine-based gas atmosphere of the above concentration, for example, a substrate processed into a predetermined shape.
  • the fluoridation treatment time varies depending on the type and size of the treated material, but is usually from ten minutes to several hours.
  • the above fluorinated substrate is subjected to a gas carburizing treatment in a carburizing gas atmosphere containing carbon monoxide at a temperature of 400 to 500, preferably at a temperature of 400 to 480. .
  • carbon monoxide is used as a carbon source gas, and is usually used in the form of a mixed gas of carbon monoxide, hydrogen, carbon dioxide, and nitrogen.
  • the gas carburizing temperature is set to a low temperature of 400 to 500
  • crystalline chromium carbides such as Cr 23 C 6 do not precipitate in the carburized hardened layer, and the chromium atoms in the austenitic stainless steel are not consumed, resulting in excellent corrosion resistance of the carburized hardened layer. Can be maintained.
  • the carburizing temperature is low, the carburizing process does not cause the coarsening of the crystalline chromium carbides such as Cr 23 C 6, Cr 7 C 3 and Cr 3 C 2 , and Little decrease in strength due to softening inside stainless steel.
  • a carburized hardened layer (a carbon diffusion and permeation layer) is uniformly formed on the surface of a substrate made of austenitic stainless steel.
  • the carburized hardened layer is originally made of austenitic stainless steel. Maintains the same level of corrosion resistance as has excellent corrosion resistance.
  • a pickling treatment is applied to the decorative article base material, for example, a base material for a watch exterior component, which has been subjected to the above-described gas carburizing treatment.
  • the base material for watch exterior parts is immersed in an acidic solution.
  • the acidic solution used in this pickling treatment is not particularly limited, and examples thereof include hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, and ammonium fluoride. These acids can be used alone, but a mixture of ammonium fluoride and nitric acid or a mixture of nitric acid and hydrofluoric acid Liquid, mixed liquid of nitric acid and hydrochloric acid, and mixed liquid of sulfuric acid and nitric acid can also be used.
  • a mixed solution of nitric acid and hydrochloric acid may have a nitric acid concentration of about 15 to 40% by weight and a hydrochloric acid concentration of about 5 to 20% by weight. preferable.
  • the concentration of the nitric acid solution is preferably about 10 to 30% by weight.
  • these acidic solutions can be used at normal temperature or at high temperature.
  • an electrolytic treatment using an electrolytic solution such as nitric acid or sulfuric acid may be performed.
  • the immersion time in the acidic solution depends on the type of the acidic solution, but is usually about 15 to 90 minutes.
  • This pickling treatment oxidizes and dissolves the iron contained in the black scale due to the carburizing process formed on the surface of the base material for the watch exterior part, and removes the black scale. Cannot completely remove black scale. Moreover, the surface of the carburized hardened layer formed by the gas carburizing treatment is roughened by dissolving iron by immersion in an acidic solution.
  • a base material for decorative articles for example, a base material for a watch exterior part is subjected to a water washing treatment.
  • the surface of the decorative article base material for example, the base material for watch exterior parts, which has been subjected to the water washing treatment, is subjected to barrel polishing.
  • a base material for a watch exterior part is placed inside a barrel tank of a barrel polishing apparatus, and preferably walnut chips and an alumina-based abrasive are put into the barrel tank as a polishing medium. Then, barrel polishing is performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized hardened layer and the remaining black scale are polished.
  • the black scale formed on the surface of the base material for watch exterior parts can be completely removed. Even if the base material for a watch exterior part has a complicated shape, the black scale can be completely removed. In addition, the surface of the base material for a watch external part can be made a mirror surface by this barrel polishing. If puff polishing is performed instead of barrel polishing, it is very difficult to completely remove the black scale formed on the surface of the base material for watch exterior parts.
  • the surface hardness (H V) of the carburized layer after barrel polishing is 500 or more under a load of 50 g
  • the hardness of a decorative article such as a watch exterior part is sufficient.
  • it should be at least 600 with a load of 50 g.
  • the surface of the base material for decorative articles such as the base material for watch exterior parts which has been barrel-polished may be further puff-polished.
  • the surface hardness (HV) of the carburized layer after such puff polishing is 50 g load. If it is 500 or more, it is sufficient for the hardness of decorative articles such as watch exterior parts. Preferably, it should be at least 600 with a load of 50 g.
  • a coating made of a nitride, carbide, oxide, nitrocarbide or nitrocarboxylate of an element of Groups 4a, 5a and 6a of the periodic table is desirable. .
  • a carbon hard coating is particularly preferable.
  • An intermediate layer can be formed between the carbon hard coating and the surface of the cured layer of the substrate.
  • Such an intermediate layer is composed of a lower layer made of Ti or Cr formed on the surface of the cured layer of the base material and an upper layer made of Si or Ge formed on the surface of the lower layer.
  • a middle class is preferred.
  • At least two types of hard coatings may be formed on the surface of the cured layer of the base material, or may be laminated.
  • the hard coating may be formed on a part of the surface of the cured layer of the base material.
  • the hard coating constituting the decorative article according to the present invention may be a coating having a color tone different from the color tone of the surface of the base material.
  • the surface hardness of the hard coating is usually larger than the surface hardness of the substrate.
  • a specific method for forming the hard coating as described above and a specific method for forming the intermediate layer provided between the carbon hard coating and the surface of the cured layer of the substrate will be described in Example A described later.
  • a gold alloy coating may be further formed on the hard coating.
  • a coating made of an alloy of gold and gold is desirable.
  • Example A A specific method for forming the gold alloy film as described above will be described in Example A described later. Next, a watch exterior component and a method of manufacturing the same according to the present invention will be specifically described.
  • the watch exterior part according to the present invention is roughly classified into a watch band formed by connecting a plurality of stainless steel pieces with a plurality of stainless steel connection parts, and a watch exterior part other than the watch band. .
  • At least the pieces constituting the former watch band and the connecting parts are subjected to carburizing treatment, particularly preferably gas carburizing treatment, and a carburized hardened layer is formed on the surface.
  • watch exterior parts other than the latter watch band are also subjected to carburizing treatment, particularly preferably gas carburizing treatment, and a carburized hardened layer is formed on the surface.
  • the elasticity of the length adjustment pin may change due to the formation of the carburized hardened layer.In such a case, the length adjustment pin may become difficult to pull out or vice versa. There is. In such a case, it is preferable to replace the carburized length-adjusting pin with a non-carburized length-adjusting pin after passing through the norrell polishing process and further the puff polishing process.
  • At least the pieces and at least the connecting parts constituting the former wristwatch band are subjected to carburizing treatment, particularly preferably gas carburizing treatment, to form a carburized hardened layer on the surface.
  • carburizing treatment particularly preferably gas carburizing treatment
  • the carburized length adjustment pins are replaced with non-carburized length adjustment pins. It points to something.
  • the watch band according to the present invention in which a plurality of stainless steel pieces are connected by a plurality of stainless steel connecting parts, after or before the plurality of pieces are connected by a plurality of connecting parts.
  • a carburizing treatment particularly preferably a gas carburizing treatment, is applied to the bridge and the connecting parts.
  • Austenitic stainless steel is particularly preferable as the stainless steel used as the material for (product).
  • the stainless steel used in the present invention does not contain titanium metal.
  • the austenitic stainless steels described above are stainless steels having an austenitic phase in an amount of 60% by weight or more at room temperature, such as Fe—Cr—Ni—Mo stainless steel and Fe—Cr—Mn stainless steel. And so on.
  • a stable stainless steel having a Ni content as small as possible is desirable from the viewpoint of the depth of the carburized hardened layer and the price, but from the viewpoint of corrosion resistance, the Ni-containing stainless steel is preferable. It is desirable to use stainless steel which has a large amount and contains about 1.5 to 4% by weight of Mo as a valuable element.
  • the most suitable austenitic stainless steel has a chromium content of 15 to 25% by weight, and is a stable stainless steel with an austenite phase stable even at room temperature. 4% by weight is added.
  • the connecting parts are obtained in order to obtain a watch exterior part having a mechanically finished surface such as a hair line engraving a large number of parallel streaks and a honing processing engraving a large number of recesses.
  • Mechanical finishing can be applied to the surface of the pieces connected by the, the pieces before connection, or the surface of the accessory base material.
  • the carburized hard layer formed on the surface of the pieces connected by the connecting parts, the pieces before connection, or the surface of the base material of the accessory is very hard, so it is very difficult to finish mechanically. It is. Also, it is convenient to perform mechanical finishing before fluoridation. No. Therefore, the mechanical finishing is performed before the fluoridation treatment.
  • the depth of the hairline, the honing recess, etc., carved on the surface of the watch or the base material for watch exterior parts other than the wristwatch band, is naturally increased by barrel polishing, which will be described later. Even after polishing, make the hair so that the hair line and honing pattern appear.
  • the depth of the concave portion of the hair line and the honing at the time of the mechanical finishing is not particularly limited, but is usually about 5 to 7 m. Also, the depth of the hairline, the honing recess, etc. after barrel polishing and further buff polishing is usually about 1 to 2 m.
  • the mechanical finishing described above can be applied to a mirror-finished polished surface by barrel polishing or puff polishing described later.
  • the concentration of dissolved carbon decreases and the hardness decreases. Therefore, the surface hardness of the carburized layer is slightly reduced by removing a region of about 1 to 2 m from the surface of the extremely hard carburized layer by barrel polishing or even puff polishing.
  • Such a polished surface may be subjected to mechanical finishing.
  • the conventional method may be used. For example, you can mask the part you want to be mirror-finished in advance and remove the masking after mechanical finishing. For example, only the unmasked part is mechanically finished, and the unmasked part has a mirror surface.
  • the hardness of the carburized layer after such mechanical finishing is 500 or more under a load of 50 g
  • the hardness of the watch exterior part is sufficient.
  • it should be at least 600 with a load of 50 g.
  • a wristwatch band according to the present invention in which a plurality of stainless steel pieces are connected by a plurality of stainless steel connecting parts, comprises a plurality of stainless steel pieces connected to a plurality of stainless steel pieces.
  • the piece and the connecting part are subjected to fluorination treatment in a fluorine-based gas atmosphere at 250 to 600, preferably 300 to 500. .
  • watch external parts other than the watch band which are formed by connecting the above pieces with connecting parts, can be used as a base material for the watch external parts (base material for watch external parts) in a fluorine-based gas atmosphere.
  • the fluorination treatment is carried out at 0 to 600, preferably at 300 to 500.
  • a fluorine-based gas is used for this fluorination treatment.
  • fluorine-based gas used herein specific examples of the preferred fluorine-based gas, and the concentration and method of use of the fluorine-based gas are described in detail in the decorative article according to the present invention and the fluorine-based gas described above in the method for producing the same. Examples, specific examples of preferred fluorine-based gas, and the same concentration and method of use of the fluorine-based gas.
  • the fluoridation treatment in the present invention is performed, for example, by processing into a predetermined shape, a stainless steel piece and a connecting part for a wristwatch band, or
  • the measuring bezel, casing, back cover, dial, etc. are placed in a furnace for fluoridation, and the test is performed at a temperature of 250 to 600 in a fluorine-based gas atmosphere having the above concentration.
  • the fluoridation time varies depending on the type and size of the processed material, but is usually from ten minutes to several tens of minutes.
  • the passivation film including C r 2 ⁇ 3 formed on the treated surface changes fluoride film. Since this fluorine film has good permeability for carbon atoms, the subsequent gas carburization process allows carbon atoms to penetrate and diffuse from the stainless steel surface into the interior, forming a carburized hardened layer easily. Can be.
  • the above-mentioned fluorinated pieces, connecting parts, or base materials for wristwatch exterior parts are placed in a carburizing gas atmosphere containing carbon monoxide at a temperature of 400 to 500T, preferably 400 to 4T. Gas carburizing is applied at 80.
  • carbon monoxide is used as a carbon source gas, and is usually used in the form of a mixed gas of carbon monoxide, hydrogen, carbon dioxide, and nitrogen.
  • the carburizing capacity (carbon potential: P c value) of this carburizing gas is generally expressed by the following equation using the partial pressure values P co and Pco 2 of C 0 and CO 2 in the gas atmosphere.
  • the gas carburizing treatment temperature by setting the gas carburizing treatment temperature to a low temperature of 400 to 500, a crystalline chromium carbide such as Cr 23 C 6 does not precipitate in the carburized hardened layer, and the austenitic system Since the chromium atoms in the stainless steel are not consumed, the excellent corrosion resistance of the carburized hardened layer can be maintained.
  • the carburizing temperature since the carburizing temperature is low, the carburizing does not cause the coarsening of the chromium carbide, and furthermore, there is little decrease in strength due to softening inside the stainless steel.
  • a carburized hardened layer (diffusion of carbon) is formed on the surface of a piece made of austenitic stainless steel and its connecting part, or the base material of a watch exterior part made of austenitic stainless steel. (Penetration layer) is formed uniformly.
  • Crystallized chromium carbides such as Cr 23 C 6 , Cr 7 C 3 , and Cr 3 C 2 were not formed in these carburized hardened layers, and according to observation with a transmission electron microscope. However, only ultrafine metal carbide having a particle size of 0.1 m or less is observed. According to spectrum analysis with a transmission electron microscope, this ultrafine metal carbide has the same chemical composition as the base metal, and is not a crystalline chromium carbide. These carburized hardened layers are formed from the same austenite phase as the base metal, with no carbon atoms forming into the dissolved metal chromium carbide in the metal lattice of the base metal.
  • the carburized hardened layer Due to the intrusion and solid solution of a large amount of carbon atoms, the carburized hardened layer has a large lattice strain. Due to the combined effect of the above ultrafine metal carbide and lattice strain, the hardness of the carburized hardened layer The hardness can be improved, and a high hardness of 700-150 pits hardness (HV) can be obtained. In addition, since the above-mentioned gas carburizing treatment does not generate crystalline chromium carbide and does not consume chromium atoms in the base metal, the carburized hardened layer has the excellent corrosion resistance inherent to austenitic stainless steel. Has the same level of corrosion resistance.
  • An ultra-thin black scale is formed on the surface of the piece after gas carburizing, its connecting part, or the base material of the watch exterior part.
  • the piece, the connecting part, or the base material for the timepiece exterior part subjected to the above-mentioned gas carburizing treatment is subjected to the same pickling treatment as the above-described acid treatment in the decorative article and the method for producing the same according to the present invention.
  • a piece, its connecting part, or a base material for a watch exterior part is immersed in an acidic solution.
  • This pickling process oxidizes and dissolves the iron contained in the black scale resulting from the carburizing process formed on the surface of the bridge, its connecting parts, or the base material for watch exterior parts, and removes the black scale.
  • this pickling treatment alone cannot completely remove black scale.
  • the surface of the piece or the like that is, the surface of the carburized hardened layer formed by the gas carburizing treatment is roughened by dissolving iron by immersion in an acidic solution.
  • the pieces, their connection parts, or the base material for watch exterior parts are subjected to a water washing treatment.
  • This washing process removes the black scale that is peeling off from the pieces, the connecting parts, or the base material for the watch exterior parts, and removes the acidic solution adhering to the pieces, the connecting parts, or the base material for the watch exterior parts. Complete The surface of the carburized hardened layer is prevented from further roughening by the acidic solution.
  • Barrel polishing is performed on the surface of the washed pieces, the connecting parts, or the base material for watch exterior parts.
  • a wristwatch band obtained by connecting pieces with connecting parts, a piece that is not connected, a connecting part, or a base material for watch exterior parts is placed inside the barrel tank of the barrel polishing machine.
  • a polishing medium preferably, walnut chips and an alumina-based abrasive are placed in a barrel tank. Then, barrel polishing is performed for about 10 hours to grind the rough surface formed on the outermost surface of the carburized hardened layer of the piece and the remaining black scale.
  • the hardness of the carburized layer after barrel polishing is 500 or more under a load of 50 g, the hardness of the watch exterior part is sufficient. Preferably, it should be at least 600 with a load of 50 g.
  • the surface of barrel-polished pieces, connected pieces, or the base material of watch exterior parts may be further buff-polished.
  • the hardness of the carburized layer after the puff polishing is 500 or more under a load of 50 g, the hardness of the watch exterior component is sufficient. Preferably, it should be at least 600 with a load of 50 g.
  • Pieces that are not connected are connected with connecting parts to complete the watch band.
  • Another watch exterior component and a method of manufacturing the same according to the present invention will be specifically described.
  • Another watch exterior part according to the present invention is made of metal, and a deformed layer including a fibrous structure in which metal crystal grains are deformed into a fibrous form is formed on the metal surface, and at least solid solution atoms are added to the deformed layer. A solid solution layer is formed.
  • the metal forming the watch exterior parts specifically, stainless steel Examples include steel, titanium metal, and titanium alloy. Among them, stainless steel, particularly austenitic stainless steel, is preferably used.
  • the deformed layer is a layer containing a fiber structure in which metal crystal grains are deformed into a fibrous shape on the metal surface. It is necessary to apply a physical external force to the The deformable layer is preferably formed by applying a physical external force that extends the surface of the metal in almost one direction.
  • Means for applying the above-mentioned physical external force to the metal surface include polishing and grinding.
  • polishing processing include conventionally known puff polishing and burnishing processing.
  • the puff polishing can be performed after the metal surface is subjected to the punishing process, and the metal surface can be subjected to the barrel polishing before the buff polishing or the varnishing process is performed on the metal surface. .
  • the metal surface can be subjected to grinding or cutting before the puff polishing or the panning process is applied to the metal surface.
  • the deformation layer is preferably formed over a depth of 2 to 100 m from the surface of the metal.
  • the hardened layer is formed by dissolving solid solution atoms on the surface of the deformation layer as described above, the metal crystal grains are still fibrous even after the hardened layer is formed. As a result, there is no step between the crystal grains and the crystal grain boundaries, so that it is impossible to visually observe the Yuzu skin. Therefore, it is necessary to obtain a watch exterior part having a smooth surface or a mirror surface. Can be. This smooth surface or mirror surface may be a flat surface or a curved surface.
  • the hardened layer is preferably formed over a depth of 5 to 50 m from the surface of the deformable layer.
  • the solid solution atom is at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, and an oxygen atom.
  • the surface hardness of the mirror surface of the cured layer is preferably Vickers hardness (HV) of 500 or more.
  • another watch exterior component includes applying a physical external force to the surface of stainless steel, and at least including the fiber structure in which metal crystal grains are deformed into a fibrous shape on the surface of the stainless steel. Form a deformation layer.
  • This deformed layer is preferably formed on the surface of the stainless steel by applying a physical external force that extends the surface of the stainless steel in almost one direction.
  • Means for applying the above-mentioned physical external force to the metal surface include polishing and grinding.
  • polishing processing include conventionally known puff polishing and burnishing processing.
  • the upper surface of the watch exterior component base material is fixed on the outer peripheral surface of the rotating wheel so that the upper surface faces outward, and then the rotating wheel is rotated to place diamond or diamond on the upper surface of the watch exterior component base material.
  • Carbide A tool for example, tungsten, carbide
  • puff polishing can be performed after the metal surface is subjected to the punishing process, and barrel polishing can be performed on the metal surface before the puff polishing or the varnishing process is performed on the metal surface.
  • the metal surface can be subjected to grinding or cutting before buffing or panning is performed on the metal surface.
  • the upper surface of the base material for a watch exterior component is pressed against a rotating grinding wheel, and the upper surface of the base material for a watch exterior component is ground by the abrasive grains of the grinding wheel.
  • cutting is performed with a reduced grinding force.
  • reducing the grinding force for example, there are methods such as smoothing the abrasive grains of a grinding wheel, reducing the number of abrasive grains, or reducing the amount of abrasive.
  • a surface of a desired shape is formed by performing at least one of a cutting process and a grinding process on the surface of the stainless steel, and then the surface of the shape is polished to form the deformed layer.
  • the surface of a stainless steel can be ground to form a surface having a desired shape and also form the deformed layer.
  • the surface having the desired shape may be a surface that is processed substantially flat, or may be a curved surface.
  • the individual means for applying a physical external force are listed in order of preference, such as burnishing, buffing, then grinding, and cutting. become.
  • the deformable layer is preferably formed over a depth of 2 to 100 / m from the surface of the stainless steel.
  • the above-mentioned deformed layer is usually formed on a stainless steel surface of a base material for a timepiece external part formed by forging (cold forging, hot forging) with a large amount of deformation.
  • a hardening treatment is performed on the surface of the deformed layer formed as described above to dissolve solid-solution atoms in a solid solution to form a hardened layer.
  • the solid solution atom at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, and an oxygen atom is used.
  • carbon atoms are dissolved in austenitic stainless steel, or nitrogen and oxygen atoms are dissolved in titanium or titanium alloy.
  • carbon atoms are dissolved in titanium or titanium alloy.
  • the hardened layer is preferably formed over a depth of 5 to 50 m from the surface of the deformable layer.
  • the surface hardness of the mirror surface of the cured layer is preferably Vickers hardness (HV) of 500 or more.
  • the hardened layer is formed by carburizing a base material for a watch exterior part made of austenitic stainless steel containing no titanium metal as a hardened layer on the surface of the deformed layer obtained as described above.
  • the watch exterior parts are manufactured through the following steps. Is preferred.
  • the base material for a watch exterior part having a deformed layer formed on the surface thereof is preferably 100 to 500, preferably 150, in a fluorine-based gas atmosphere.
  • the fluorination treatment is preferably performed at a temperature of from 300 to 300.
  • the austenitic stainless steel includes, for example, Fe—Cr—Ni—Mo stainless steel, Fe—Cr—Mn stainless steel, and the like.
  • a stable stainless steel having a Ni content as small as possible is desirable from the viewpoint of the depth of the carburized hardened layer and the price. From the viewpoint of corrosion resistance, the Ni content is preferable. It is desirable to use stainless steel containing about 1.5 to 4% by weight of Mo as a valuable element.
  • the most suitable austenitic stainless steel has a chromium content of 15 to 25% by weight, and is a stable stainless steel with an austenite phase stable even at room temperature. 4% by weight is added.
  • fluorine-based gas used in the above-mentioned fluoridation treatment preferred specific examples of the fluorine-based gas, and the concentration and method of use of the fluorine-based gas are described in the decorative article and the method for producing the same according to the present invention.
  • Specific examples of the fluorine-based gas described above, specific examples of the preferred fluorine-based gas, and the same concentrations and methods of use of the fluorine-based gas are the same.
  • a stainless steel piece for a watch band, a bezel for a watch, a casing, a back cover, a dial, etc. which is processed into a predetermined shape, is placed in a furnace for the fluoridation treatment.
  • the fluoridation time varies depending on the type and size of the processed material, but is usually from ten minutes to several hours.
  • the base material for a watch exterior component subjected to the fluorination treatment contains the gas carburizing treatment described above in the watch exterior component (including the watch band) and the method for producing the same according to the present invention, that is, carbon monoxide.
  • a gas carburizing treatment is performed at a temperature of 400 to 500, preferably at a temperature of 400 to 480, in a carburizing gas atmosphere.
  • the gas carburizing treatment temperature by setting the gas carburizing treatment temperature to a low temperature of 400 to 500, crystalline chromium carbide such as Cr 23 C 6 does not precipitate in the carburized hardened layer, and the austenitic system Since the chromium atoms in the stainless steel are not consumed, the excellent corrosion resistance of the carburized hardened layer can be maintained.
  • the carburizing temperature since the carburizing temperature is low, the carburizing does not cause the coarsening of the chromium carbide, and furthermore, there is little decrease in strength due to softening inside the stainless steel.
  • a carburized hardened layer (a carbon diffusion and permeation layer) is uniformly formed on the surface of a base material for watch exterior parts made of austenitic stainless steel.
  • the hardness of the carburized hardened layer is improved, and a high hardness of Vickers hardness (HV) of 700 to 150 can be obtained.
  • HV Vickers hardness
  • the carburized hardened layer is an excellent austenitic stainless steel inherently possessed. And the same level of corrosion resistance.
  • An ultrathin black scale is formed on the surface of the base material for watch exterior parts after gas carburizing.
  • the base material for a watch exterior part that has been subjected to the above-described gas carburizing treatment is subjected to the same pickling treatment as the above-described acid treatment in the decorative article according to the present invention and the method for producing the same.
  • This pickling treatment oxidizes and dissolves the iron contained in the black scale due to the carburizing process formed on the surface of the base material for the watch exterior part, and removes the black scale. Cannot completely remove black scale. Moreover, the surface of the carburized hardened layer formed by the gas carburizing treatment is roughened by dissolving iron by immersion in an acidic solution.
  • the base material for the watch exterior parts is subjected to a water washing treatment. You.
  • the surface of the base material for watch exterior parts that has been subjected to the water washing treatment is barrel-polished.
  • a base material for a watch exterior part is placed inside a barrel tank of a barrel polishing apparatus, and preferably walnut chips and an alumina-based abrasive are put into the barrel tank as a polishing medium. Then, barrel polishing is performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized hardened layer and the remaining black scale are polished.
  • the black scale formed on the surface of the base material for watch exterior parts can be completely removed. Even if the base material for a watch exterior part has a complicated shape, the black scale can be completely removed. In addition, the surface of the base material for a watch external part can be made a mirror surface by this barrel polishing. If puff polishing is performed instead of barrel polishing, it is very difficult to completely remove the black scale formed on the surface of the base material for watch exterior parts.
  • the surface hardness (HV) of the carburized layer after barrel polishing is 500 or more under a load of 50 g, the hardness of the watch exterior parts is sufficient. Good More preferably, it should be 600 or more with a 5 Og load.
  • the surface of the base material for watch exterior parts which has been barrel-polished may be further puff-polished.
  • the surface hardness (HV) of the carburized layer after the puff polishing is at least 500 under a load of 50 g, the hardness of the watch exterior component is sufficient. Preferably, it should be at least 600 with a load of 50 g.
  • the decorative article according to the present invention has a higher surface hardness because the hard coating is further formed on the surface of the hardened layer in which solid solution atoms are dissolved at an arbitrary depth from the surface of the base material, Excellent stickiness.
  • the decorative article according to the present invention can form a gold alloy film entirely or partially on the surface of the above-mentioned hard film, it gives various colors including gold without lowering the surface hardness. Can increase the decorative value.
  • the method for manufacturing a decorative article according to the present invention it is possible to manufacture the decorative article according to the present invention, for example, a watch exterior part, with high productivity.
  • a watch exterior made of austenitic stainless steel having excellent scratch resistance and a mirror-finished surface without impairing the excellent corrosion resistance inherent in stainless steel, particularly austenitic stainless steel.
  • Another timepiece exterior component according to the present invention may be configured such that at least a deformation layer is formed on a metal surface of a base material for a timepiece exterior component after a deformation layer including a fiber structure in which metal crystal grains are deformed into a fibrous shape is formed. Since the hardened layer is formed by dissolving solid solution atoms in the surface, it has a smooth surface or mirror surface without “yuzu skin” and has excellent appearance.
  • a base metal made of stainless steel SSUS316 was subjected to hot forging, cold forging, cutting, and drilling to create a watch band piece.
  • a connecting part is inserted into a pin hole formed in each of the pieces, and the plurality of pieces and the pieces are rotatably connected to each other. Polished with a mirror finish to complete the watch band.
  • some pieces of the wristband which consist of a large number of pieces are detachable from adjacent pieces so that the length of the band can be adjusted according to the thickness of the wrist of the wearer. This is a so-called length adjustment piece.
  • the pieces other than the length adjustment pieces are linked so that they cannot be easily separated from adjacent pieces.
  • the connecting parts used for the length adjustment pieces (length adjusting pins) and the connecting parts used for other pieces (connecting pins, split pipes and mouth-pin pins) were used.
  • the wristwatch band was placed in a metal Matsufur furnace and heated to 480.
  • a fluorine-based gas (a mixed gas of 5% by volume of NF 2 and 95% by volume of 1 ⁇ 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • Black scale was formed on the surface of the removed carburized band. Next, this band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the piece was polished. As a result, a region at a depth of 1 to 2 m from the surface of the carburized layer was removed, and the surface of the bridge, that is, the outermost surface of the carburized layer became a mirror surface.
  • the obtained wristwatch band having a mirror surface was excellent in scratch resistance and retained corrosion resistance equivalent to the excellent corrosion resistance inherent in the SUS316-based material.
  • the surface hardness (H V) of the carburized layer reached 700 under a load of 50 g.
  • connecting parts were also carburized, a hard carburized layer was formed in a region several dozen xm deep from the surface of the connecting parts. As a result, the hardness of the connecting parts increases, and even if the band is pulled along the longitudinal direction of the band, the connecting pins and the length adjusting pins are not easily bent or broken. It's gone.
  • connecting parts such as connecting pins and length adjusting pins remain in the pin holes formed in each piece, even if pickling processing or polishing processing is performed, black parts formed on the connecting parts are not removed. The skin is difficult to remove. If black scale remains on the connected parts after pickling or polishing, the connected parts with black scales may be replaced with new ones. By performing such a replacement, a band in which only the connection part is not formed with the carburized layer is obtained.
  • a gold-colored hard coating is formed on the carburized layer of each piece.
  • a TiN consisting of titanium nitride as a golden hard film was formed by an ion plating method, one of the dry plating methods.
  • Coating 3 is formed.
  • the band on which the carburized layer 2 was formed was washed with an organic solvent such as isopropyl alcohol, and placed in an ion plating apparatus. Since the ion pretending device may be a commonly used device, its description is omitted, including the drawings.
  • the inside of the apparatus was evacuated to 1.0 X 10 — 5 Torr, and argon gas was introduced as an inert gas to 3.0 X 10 — 3 Torr.
  • an argon plasma was formed by driving the thermionic filament and the plasma electrode provided inside the apparatus. At the same time, a potential of ⁇ 50 V was applied to the band, and bombard cleaning was performed for 10 minutes.
  • the surface hardness (HV) of the piece 1 coated with the TiN coating 3 reached 800 under a load of 50 g.
  • the bridge 1 coated with the TiN coating 3 had excellent wear resistance, corrosion resistance, and scratch resistance.
  • the piece 1 that has been subjected to the surface hardening treatment is further less damaged.
  • the dry plating method is not limited to the above-described ion plating method, and a known method such as a sputtering method or a vacuum deposition method can be used.
  • a golden hard coating formed by the dry plating method elements of the 4a, 5a, and 6a groups of the periodic table (Ti, Zr, HfV, Nb, Ta, Cr, M o, W), a coating made of a nitride, carbide, oxide, nitrogen carbide or carbonitride can be employed.
  • the value of X indicating the degree of nitridation becomes smaller than 1;
  • the color of the coating of the object MN x approaches from gold to pale yellow.
  • the gold color of the coating becomes reddish. If the value of X indicating the degree of nitridation is in the range of 0.9 to 1.1, a gold color close to the color tone of gold or a gold alloy can be formed on the nitride MNx film.
  • the nitride of M MN x is a hard coat with sufficient hardness, and at the same time, the gold color closest to the color tone of gold or gold alloy Present.
  • the degree of carbonization, oxidation, and nitridation must be controlled within the specified ranges. Thereby, the gold color closest to the color tone of gold or gold alloy can be given to those films.
  • the TiN coating and the ZrN coating are preferable because they are hard coatings having sufficient hardness and at the same time exhibit a gold color closest to the color tone of gold or a gold alloy.
  • the film thickness of the M nitride MNx film is preferably controlled in the range of 0.1 to 10 zm, more preferably in the range of 0.2 to 5 Atm.
  • Example A1 On the bridge on which the carburized layer was formed by the same method as in Example A1, a hard coating having a color tone different from that of Example A1 was formed.
  • a TiC coating 4 made of titanium carbide is formed as a white-colored hard coating by a dry plating method.
  • TiC film 4 was evaporated in an ethylene gas atmosphere to form a TiC film 4 on the surface of the band piece 1.
  • Other film forming conditions were the same as in Example A1.
  • the band thus obtained exhibited a uniform white tone due to the formation of the TiC coating 4. This further enhanced the decorative value of the band.
  • the surface hardness (HV) of the bridge 1 coated with the TiC coating 4 reached 800 with a load of 50 g.
  • the piece 1 covered with the coating 4 had excellent wear resistance, corrosion resistance, and scratch resistance.
  • a carbon hard coating is formed as a hard coating having a black color tone on a bridge on which a carburized layer is formed by the same method as in Example A1.
  • Hard carbon coatings are widely known as diamond * like carbon (DLC) because of their excellent properties similar to diamond.
  • a black carbon hard coating 5 is formed on the carburized layer 2 formed on the surface of the band piece 1 by a dry plating method.
  • the method for forming the carbon hard coating 5 is, for example, as follows.
  • the band on which the carburized layer 2 was formed was washed with an organic solvent such as isopropyl alcohol and placed in a vacuum device. Then, using a high-frequency plasma CVD method, a carbon hard coating 5 was formed on the carburized layer 2 to a thickness of 2 / m under the following conditions.
  • the carbon hard coating 5 was formed on the carburized layer 2 with good adhesion.
  • the band obtained as described above exhibited a uniform black tone due to the formation of the carbon hard coating 5. This further increased the decorative value of the band.
  • the surface hardness (HV) of the bridge 1 coated with the carbon hard coating 5 reached 300000 to 500.000.
  • carburized layer 2 is harder
  • the piece 1 that has been subjected to a surface hardening treatment (carburizing treatment) is further less likely to be damaged.
  • the thickness of the carbon hard coating 5 is controlled preferably in the range of 0.1 to 5 m, more preferably in the range of 0.5 to 3 m.
  • various vapor phase film forming methods such as a DC plasma CVD method and an ECR method can be used in addition to the RFP—CVD method.
  • a physical vapor deposition method such as an ion beam method, a sputtering method, or an ion plating method may be employed.
  • an intermediate layer coating 6 between the carburized layer 2 and the carbon hard coating 5 because the carbon hard coating 5 adheres more strongly to the surface of the bridge 1.
  • the method of forming the intermediate layer coating 6 is, for example, as follows.
  • a coating 63 was formed on the carburized layer 2 to a thickness of 0.1 lm by a dry plating method, for example, a sputtering method. Further, an Si film 6b was formed on the Ti film 6a to a thickness of 0.3 by a sputtering method.
  • the carbon hard coating 5 may be formed with a thickness of 2 // m on the Si coating 6 b using, for example, a high-frequency plasma CVD method according to the above-described conditions.
  • the Ti coating 6a can be replaced with a chromium (Cr) coating.
  • the Si coating 6b can be replaced with a germanium (Ge) coating.
  • the intermediate layer (coating) may be a single layer of a carbide of a Group IVa or Group Va metal in addition to such a laminated coating.
  • a carbide of a Group IVa or Group Va metal in addition to such a laminated coating.
  • excessive Titanium carbide coatings containing carbon are preferred because of their high adhesion strength to carbon hard coatings.
  • a hard film having a golden tone is formed on a part of the surface of the piece on which the carburized layer is formed by the same method as in Example A1.
  • a TiN film 7 made of titanium nitride was formed on a part of the surface of the band piece 1 as a hard film with a golden color tone by the ion plating method, which is one of the dry plating methods. Is done.
  • an organic masking agent or a masking ink made of an epoxy resin is printed on a desired portion of the surface of each of the pieces 1 on which the carburized layer 2 is formed, and the masking layer 8 is formed. Formed. Next, the band piece 1 on which the masking layer 8 was formed was washed with an organic solvent such as isopropyl alcohol and placed in an ion plating apparatus.
  • the ion preting apparatus may be a commonly used apparatus, and a description thereof will be omitted including the drawings.
  • argon gas was introduced a inert gas to 3. 0 X 1 0 _ 3 T orr.
  • argon plasma was formed by driving thermionic filaments and plasma electrodes provided inside the apparatus. At the same time, a potential of ⁇ 50 V was applied to each of the pieces 1 of the band, and bombard cleaning was performed for 10 minutes.
  • nitrogen gas was introduced into the apparatus up to 2.0 ⁇ 10 3 Torr. After the plasma was generated by the plasma gun provided inside the device, the titanium was evaporated for 10 minutes, and as shown in Fig. 6, a TiN film was formed on the surface of the hardened layer 2 of each of the band pieces 1.
  • a TiN film 7a was formed on both the surface of the mask layer 7 and the masking layer 8 to a thickness of 0.5 m.
  • the masking layer 8 is swollen with a stripping solution obtained by adding formic acid and hydrogen peroxide to ethyl methyl ketone (EMK) or ethyl methyl ketone (EMK).
  • EMK ethyl methyl ketone
  • EK ethyl methyl ketone
  • a mechanical masking means may be used in addition to providing the chemical masking layer as described in this embodiment. That is, before forming the titanium nitride (TiN) film, a metal cap may be put on an arbitrary portion of the piece in advance, and after forming the titanium nitride film, the cap may be removed. According to such a masking method, the portion of the piece covered with the cap is not covered with the titanium nitride film, and the portion not covered with the cap is covered with the titanium nitride film.
  • the titanium nitride coating was used as the hard coating formed partially on the surface of the bridge 1, but as described in the embodiment A1.
  • a coating made of a nitride, carbide, oxide, nitrocarbide or nitrocarboxylate of a 4a, 5a or 6a group element of the periodic table may be employed. it can.
  • Example A2 when the titanium carbide coating used in Example A2 was partially formed on the surface of the bridge 1, a portion exhibiting a white color with the titanium carbide coating formed thereon and a stainless steel having no titanium carbide coating formed thereon A piece having a silver-white portion is obtained.
  • Example A5 when the carbon hard coating used in Example A3 is partially formed on the surface of the piece 1, a black color tone portion where the carbon hard coating is formed and a stainless steel where the carbon hard coating is not formed are formed. A piece having a silver-white portion of steel is obtained.
  • Example A 5 When the carbon hard coating used in Example A3 is partially formed on the surface of the piece 1, a black color tone portion where the carbon hard coating is formed and a stainless steel where the carbon hard coating is not formed are formed. A piece having a silver-white portion of steel is obtained.
  • a gold-colored hard coating is formed on the surface of the piece on which the carburized layer has been formed in the same manner as in Example A1. Further, a gold alloy film is formed on the gold hard film.
  • a TiN consisting of titanium nitride, which is a gold hard film, was formed by the ion plating method, which is one of the dry plating methods.
  • a coating 9 is formed on the TiN film 9, a gold-titanium alloy film 10 is formed as a gold alloy film.
  • an argon plasma was formed by driving the thermionic filament and the plasma electrode provided inside the apparatus. At the same time, a potential of ⁇ 50 V was applied to each of the pieces 1 of the band, and bombardment was performed for 10 minutes.
  • titanium was evaporated for 10 minutes to form a Ti i coating 9 on the entire surface of the piece 1 with a thickness of 0.5 m.
  • the band pieces thus obtained had a uniform golden tone. This has increased the decorative value of the band.
  • a gold-titanium alloy film 10 as the outermost layer film, a band exhibiting a warmer golden color tone than the TiN film 9. was gotten. This further enhanced the aesthetics of the band.
  • a gold alloy coating itself cannot achieve effective wear resistance, corrosion resistance, or scratch resistance unless it has a thickness exceeding 10 x m.
  • Gold is a very expensive metal. Therefore, forming such a gold alloy coating thicker would significantly increase the cost of the coating.
  • a hard TiN coating was provided under the outermost coating made of a gold alloy coating. Since the TiN coating has excellent wear resistance, corrosion resistance, and scratch resistance, the outermost coating made of a gold alloy coating can be made thin. In this embodiment, it is said that by forming a TiN film and forming a thin gold alloy film thereon, the amount of expensive gold used is reduced, and the cost of the film can be reduced. There are advantages.
  • the outermost coating of the thin gold alloy coating may be partially worn away, exposing the underlying TiN coating, but any localized wear of the outermost coating may also occur. It is never noticeable. This is because the TiN film has optical properties similar to gold and has a golden color tone. The TiN film of the same golden color appears from under the worn part of the outermost layer of the gold-colored gold alloy film. Therefore, even if the outermost coating made of a gold alloy coating is thinned, its wear is not observed, and the aesthetic appearance and decorative value of the band as an accessory can be maintained.
  • a titanium nitride film was used as the hard film, but in addition, a gold hard film formed by a dry plating method was used. Coatings composed of nitrides, carbides, oxides, carbonitrides, or carbonitrides of the elements in Groups 4a, 5a, and 6a of the Periodic Table can be used.
  • A, Si, V, Cr, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Hf, Ta, W, Ir, and at least one metal selected from Pt A film made of an alloy of iron and gold can be formed.
  • an organic masking agent made of an epoxy resin or a masking ink is printed on a desired portion of the surface of each of the pieces 1 on which the carburized layer 2 is formed, and the masking layer 8 is formed. Formed. Next, the band piece 1 on which the masking layer 8 was formed was washed with an organic solvent such as isopropyl alcohol and placed in an ion plating apparatus.
  • the TiN coatings 11 and 11 were applied to the surface of the carburized layer 2 of the band piece 1 and the surface of the masking layer 8. It was formed with a thickness of 0.5 m.
  • gold-titanium alloy coatings 12, 12a were formed on the TiN coatings 11, 11a to a thickness of 0.3 m.
  • the masking layer 8 is swollen with a stripping solution in which formic acid and hydrogen peroxide are added to ethyl methyl ketone (EMK) or ethyl methyl ketone (EMK), and the masking layer 8 is lifted off.
  • EK ethyl methyl ketone
  • EK ethyl methyl ketone
  • EK ethyl methyl ketone
  • a first hard coating is formed on the surface of the bridge on which the carburized layer has been formed in the same manner as in Example A1. Further, a second hard coating having a color tone different from that of the first hard coating is formed on a part of the surface of the first hard coating.
  • a first hard coating a TiN coating 3 made of gold-colored titanium nitride, which is a first hard coating, was formed on the surface of the piece 1 on which the carburized layer 2 was formed by the same method as in Example A1. Formed. A masking layer 13 was formed on a desired portion of the surface of the TiN coating 3 by printing an organic masking agent made of an epoxy resin or a masking ink.
  • a second hard coating i.e., a TiC coating 14 made of white-colored titanium carbide, was formed on the surface of the TiN coating 3 by the same method as in Example A2.
  • a TiC film 14a was formed on the surface of the masking layer 13.
  • the masking layer 13 was swollen with a peeling solution, and the masking layer 13 and the TiC film 14a laminated thereon were peeled off by a lift-off method.
  • a band piece having a portion exhibiting the specified golden tone is obtained. This further enhances the decorative value of the band I was able to.
  • the piece 1 subjected to the surface hardening treatment (carburizing treatment) is further less likely to be damaged.
  • various hard coatings other than the titanium nitride and titanium carbide coatings can be used as the hard coating in this embodiment.
  • either the first hard coating or the second hard coating can be the carbon hard coating described in Example A3.
  • the type of the masking layer 13 and the type of the stripping solution can be appropriately selected according to the type of the coating.
  • the first hard coating and the second hard coating are both MNX coatings. You can also. In this case, if each hard coating is formed so that the value of X indicating the degree of nitridation in the first hard coating is different from the value of X in the second hard coating, the first hard coating and the second hard coating are formed.
  • the hard coating can be formed to have a different color tone. The same applies to carbides, oxides, carbides, and carbonitrides.
  • a first hard coating is formed on a part of the surface of the bridge on which the carburized layer is formed by the same method as in Example A1. Further, a second hard coating having a color tone different from that of the first hard coating is formed on another part of the surface of the piece.
  • Example A4 As shown in FIG. 14, by the same method as in Example A4, a part of the surface of the piece 1 on which the carburized layer 2 was formed A TiN film 7 made of titanium nitride was prepared. A masking layer 15 was formed on a desired portion of the surface of the TiN coating 7 and the surface of the piece 1 continuous with the mask.
  • the surface of the TiN coating 7, the masking layer 15 and the remaining piece 1 were coated with a white color tone as a second hard coating by the same method as in Example A2.
  • a TiC film 16 made of titanium carbide was formed.
  • the masking layer 15 was swollen with a peeling solution, and the masking layer 15 and the TiC film 16 laminated thereon were peeled off by a lift-off method.
  • Example A7 The options of the first hard coating and the second hard coating, or the options of the stripping solution and the masking layer are as described in Example A7. Further, the gold alloy coating film described in Example A5 may be formed on one or both of the first hard coating film and the second hard coating film.
  • the ion plating method was used as the dry plating method, but a known film forming means such as a sputtering method or a vacuum evaporation method can be used. .
  • the pieces of the band of the wristwatch have been described as examples.
  • the invention does not The present invention can also be applied to a device containing a mechanical or electronic drive mechanism.
  • the present invention can be applied to any other decorative articles (including parts).
  • Example B 1 [Example of watch exterior part and method for manufacturing the same according to the present invention]
  • a base metal made of stainless steel SSUS316 was subjected to hot forging, cold forging, cutting, and drilling to create a watch band piece.
  • a connecting part is inserted into a pin hole formed in each piece, the plurality of pieces and the pieces are rotatably connected to each other, and the surfaces of the pieces are polished by buffing or the like to finish a mirror surface, and the watch Completed the band.
  • Some pieces of the wristwatch band which are made up of a number of pieces, are detachable from adjacent pieces so that the length of the band can be adjusted according to the thickness of the wrist of the wearer.
  • This is a so-called length adjustment piece, and pieces other than the length adjustment piece are pieces that are connected so that they cannot be easily separated from adjacent pieces.
  • the connecting parts used for the length adjustment pieces length adjustment pins
  • connection pins, split pipes, and knurled pins were used.
  • the band of the wristwatch was placed in a metal pine full furnace, and the temperature was raised to 48.
  • a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • a carburizing gas (1 0% by volume C_ ⁇ , 1 to 2 0% by volume [2, and 1 volume% of C 0 2, 6 9% by volume 1 ⁇ blowing a mixed gas) and 2, after performing the carburizing treatment and held for 12 hours at 4 8 0, was taken out band from Matsufuru furnace.
  • Black scale was formed on the surface of the removed carburized band. Next, this band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • black scale is also used on the opposing surfaces of the adjacent pieces, the inner wall of the pin hole, and the connecting pins, split pipes, and length adjustment pins that connect the pieces to each other. Not observed.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the piece was polished. As a result, a region of 1 to 2 zm depth from the surface of the carburized layer was removed, and the surface of the piece, that is, the outermost surface of the carburized layer became a mirror surface.
  • the obtained mirror surface of the wristwatch band has excellent scratch resistance, and the excellent corrosion resistance inherent to SUS316-based material. Equivalent corrosion resistance was maintained.
  • Each of the above-mentioned processing steps was performed after a large number of pieces were put together in the form of a band, so that the labor and time required for the processing work were reduced, and the processing cost was reduced.
  • the connecting parts were carburized, a hard carburized layer was formed at a depth of several tens of meters from the surface of the connecting parts. As a result, the hardness of the connecting part was increased, and the connecting pin and the length adjusting pin were less likely to bend or break even when the band was pulled along the longitudinal direction of the band.
  • Example B1 a number of hair lines along the band length direction were formed on the front surface of the band piece (the surface facing outward when worn on the wrist) before performing the fluoridation treatment.
  • a wristwatch band was obtained in the same manner as in Example B1, except for the following.
  • the surface of the band of the obtained wristwatch had a hair-line finish, was excellent in scratch resistance, and maintained corrosion resistance equivalent to the excellent corrosion resistance inherent in the SUS316-based material.
  • Example B1 a wristwatch bezel is used instead of a wristwatch band.
  • a mirror-finished bezel was obtained in the same manner as in Example B1, except that a bezel was used.
  • the obtained bezel had excellent scratch resistance and retained corrosion resistance equivalent to the excellent corrosion resistance inherent to the SUS316-based material.
  • a mirror-finished casing was obtained in the same manner as in Example B1, except that a wristwatch case was used in place of the wristwatch band.
  • Example B 5 The obtained casing had excellent scratch resistance, and retained corrosion resistance equivalent to the excellent corrosion resistance inherent to the SUS316-based material.
  • Example B1 a mirror-finished back cover was obtained in the same manner as in Example B1, except that a watch back cover was used instead of the watch band.
  • a mirror-finished dial was obtained in the same manner as in Example B1, except that a dial for a wristwatch was used instead of the band of the wristwatch in Example B1.
  • the dial obtained has excellent scratch resistance and is originally made of SUS316-based material. Corrosion resistance equivalent to the excellent corrosion resistance possessed was maintained.
  • a rod-like material made of austenitic stainless steel SUS316 series was prepared.
  • the cross section of this rod-shaped material is rounded and rectangular so as to match the shape of the watch band piece.
  • This rod-shaped material was cut to the width of the band piece.
  • a connecting pin was inserted into a pin hole formed in each piece, and a plurality of pieces and the pieces were rotatably connected to each other to assemble a wristwatch band.
  • the rounded upper surface of each piece of the watch band was puffed.
  • the wristwatch band was placed in a metal Matsufur furnace and heated to 480. Then, a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of ⁇ 2 ) was introduced into the Matsufur furnace for 15 minutes. Blowing and fluoridation were performed.
  • a fluorine-based gas mixed gas of 5% by volume of NF 2 and 95% by volume of ⁇ 2
  • Black scale was formed on the surface of the removed carburized band. Next, this band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the piece was polished.
  • the column was cold forged so as to apply an external force along a central axis passing through the center of the circular cross section of the column, and the column was forged into the shape of a watch band piece.
  • a connecting pin was inserted into a pin hole formed in each piece, and a plurality of pieces and pieces were rotatably connected to each other to assemble a wristwatch band.
  • the upper surface of each piece of the wristwatch band (the front surface facing outward when worn on the wrist) was flat mirror-finished by panitizing. That is, after fixing the band so that the upper surface of the band faces outward on the outer peripheral surface of the wheel, the wheel was rotated and a diamond tool was pressed against the upper surface of the band.
  • the deformed layer containing such a fiber structure is 5 to 10 m over a depth of m.
  • the wristwatch band was charged into a metal Matsufur furnace and then heated to 48 Ot :.
  • a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • a carburizing gas (1 0% by volume of CO, and 2 0% by volume of H 2, 1% by volume (: and ⁇ 2, 6 9 volume% 1 ⁇ 2
  • the mixture was blown and kept at 480 for 12 hours to carry out carburizing treatment, and then the band was taken out of the Matsufur furnace.
  • Black scale was formed on the surface of the removed carburized band. Next, this band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. And barrel polishing takes about 10 hours, The rough surface formed on the outermost surface of the carburized layer of the piece was polished.
  • a wristwatch band was assembled in the same manner as in Example C2.
  • Example 1 When the cross section of the upper surface of the piece obtained as described above was observed with an electron microscope, the metal grains on the stainless steel surface were rotated by the external force applied by the puff polishing, as in Example 1. It was confirmed that the fiber structure was stretched along the direction and deformed into a fibrous form. The deformed layer containing the fibrous structure was formed over a depth of 3 to 6 m from the upper surface of the bridge.
  • the wristwatch band was charged into a metal Matsufur furnace and then heated to 480.
  • a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of 1 ⁇ 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • a carburizing gas (1 0% by volume of CO, and 2 0% by volume of? 1 2, 1 volume% and (3 0 2, 6 9 volume% N 2 and The mixture was then carburized by holding at 480 for 12 hours, and then the band was taken out of a Matsufur furnace.
  • Black scale was formed on the surface of the removed carburized band. Next, this band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the piece was polished.
  • a wristwatch band was assembled in the same manner as in Example C2.
  • each piece of the wristwatch band was made a flat mirror surface by grinding with reduced grinding force. That is, the upper surface of the wristwatch band was pressed against the rotating grinding wheel, and the upper surface of each piece was ground with the abrasive grains of the grinding wheel.
  • each piece was further polished by puff polishing to a mirror surface.
  • Example C1 When the cross section of the upper surface of the piece obtained as described above was observed with an electron microscope, as in Example C1, the external force applied by the grinding and puff polishing caused the metal grains on the stainless steel surface to become a whetstone. It was confirmed that the fiber structure was stretched along the direction of rotation of the car and puff and was transformed into a fibrous structure. Is the deformed layer containing such a fiber tissue from the top of the piece? Formed over a depth of ⁇ 12.
  • the wristwatch band was charged into a metal Matsufur furnace and then heated to 480.
  • a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • the carburizing gas (10% by volume) And CO, and 2 0% by volume of 1 ⁇ 2, and 1 volume% of C 0 2, 6 9% by volume: blowing a mixed gas) with 2, 1 2 hour hold to carburizing 4 8 0
  • the band was taken out of the Matsufur furnace.
  • Black scale was formed on the surface of the removed carburized band. Next, this band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the piece was polished.
  • Example C4 the upper surface of each piece can be made a flat mirror surface and the metal crystal grains in the vicinity of the surface can be changed into a fiber structure by grinding with reduced grinding force, so that the number of manufacturing steps can be reduced. Can be. Therefore, by employing such a grinding process, the manufacturing cost can be reduced.
  • Example C 5 the upper surface of each piece can be made a flat mirror surface and the metal crystal grains in the vicinity of the surface can be changed into a fiber structure by grinding with reduced grinding force, so that the number of manufacturing steps can be reduced. Can be. Therefore, by employing such a grinding process, the manufacturing cost can be reduced.
  • a wristwatch band was assembled in the same manner as in Example C2.
  • each piece of the wristwatch band was made a flat mirror surface by grinding with reduced grinding force. That is, the upper surface of the wristwatch band was pressed against the rotating grinding wheel, and the upper surface of each piece was ground with the abrasive grains of the grinding wheel.
  • the metal crystal grains on the stainless steel surface were stretched along the rotating direction of the grinding wheel with reduced grinding force, and the fiber It was confirmed that the fiber structure was deformed into a shape.
  • the deformed layer containing such a fiber tissue was formed at a depth of 2 to 5 m from the upper surface of the bridge.
  • the wristwatch band was charged into a metal Matsufur furnace and then heated to 480.
  • a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • a carburizing gas (1 0% by volume of CO, and 1 ⁇ 2 0 volume%, and 1 vol% 0 0 2, and 6 9 volume% of N 2 Gas
  • Black scale was formed on the surface of the removed carburized band. Then, the band was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the band piece that is, the surface of the carburized layer formed by carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the washed band was placed inside a barrel tank of a barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the piece was polished.
  • each piece can be made a flat mirror surface and the metal crystal grains near the surface can be changed into a fiber structure by grinding with reduced grinding force, so that the number of manufacturing steps can be reduced. Can be. Therefore, by employing such a grinding process, the manufacturing cost can be reduced.
  • Example C 6
  • the cylinder was cold forged so as to apply an external force along a central axis passing through the center of the circular cross section of the cylinder, and the cylinder was forged into an annular member.
  • this member was buffed to complete a bezel having a mirror-finished upper surface.
  • the external force applied by the buff polishing causes the metal crystal grains on the stainless steel surface to be stretched along the direction in which the puff rotates, resulting in a fibrous deformation. It was confirmed that the fiber structure was obtained.
  • the deformed layer containing the fibrous structure was formed at a depth of 3 to 5 m from the upper surface of the bezel.
  • the bezel was charged into a metal pine full furnace and heated to 480.
  • a fluorine-based gas (mixed gas of 5% by volume of NF 2 and 95% by volume of 1 ⁇ 2 ) was blown into the Matsufuru furnace for 15 minutes to perform a fluorination treatment.
  • a black scale was formed on the surface of the removed carburized bezel.
  • this bezel was immersed in an acidic aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 minutes.
  • the surface of the bezel that is, the surface of the carburized layer formed by the carburizing treatment, had a rough surface because iron was dissolved by immersion in an acidic aqueous solution.
  • the rinsed bezel was set inside the barrel tank of the barrel polishing apparatus, and walnut chips and an alumina-based abrasive were put into the barrel tank as a polishing medium. Then, barrel polishing was performed for about 10 hours, and the rough surface formed on the outermost surface of the carburized layer of the bezel was polished.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
PCT/JP2000/006086 1987-08-12 2000-09-07 Ornement et son procede de preparation WO2001018275A1 (fr)

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EP00956994A EP1146136B1 (en) 1999-09-07 2000-09-07 Ornament and method for preparation thereof
US09/831,327 US6905758B1 (en) 1987-08-12 2000-09-07 Decorative item and process for producing the same
HK02101696.3A HK1040421B (zh) 1999-09-07 2002-03-05 裝飾品及其製造方法

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Application Number Priority Date Filing Date Title
JP11/252900 1999-09-07
JP25290099A JP4350225B2 (ja) 1999-09-07 1999-09-07 時計外装部品およびその製造方法
JP31943799A JP4463353B2 (ja) 1999-11-10 1999-11-10 時計外装部品およびその製造方法
JP11/319437 1999-11-10
JP2000104454A JP4451536B2 (ja) 2000-04-06 2000-04-06 装飾部材およびその製造方法
JP2000/104454 2000-04-06

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CN103215603A (zh) * 2013-05-13 2013-07-24 西南大学 电解腐蚀在提高硬质涂层与金属或合金基体结合强度中的应用
CN103266322B (zh) * 2013-05-28 2015-02-11 福建钢泓金属科技有限公司 一种真空沉积高硬滑爽不锈钢镜面装饰板
CN103361593A (zh) * 2013-06-21 2013-10-23 燕山大学 表面强化锆材料及其无氢渗碳镀方法
CN105385983B (zh) * 2015-11-09 2017-10-24 中国矿业大学 一种以纳米碳材料的热扩散为预处理的硬质涂层制备方法
CN108882598A (zh) * 2018-09-03 2018-11-23 维达力实业(深圳)有限公司 复合盖板及其制备方法
JP6839884B2 (ja) * 2019-03-05 2021-03-10 国立大学法人東海国立大学機構 ダイヤモンド切削工具を用いた切削方法
CN113885303B (zh) * 2021-10-27 2022-08-23 东莞得利钟表有限公司 一种利用航天发射器回收料制作手表壳件的工艺
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CN100374613C (zh) 2008-03-12
KR20010085998A (ko) 2001-09-07
EP1146136B1 (en) 2011-06-22
KR100754811B1 (ko) 2007-09-04
HK1040421B (zh) 2011-11-18
EP1146136A1 (en) 2001-10-17
EP1146136A4 (en) 2006-09-06
HK1040421A1 (en) 2002-06-07

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