WO2016104329A1 - 時計ネジおよびその製造方法 - Google Patents
時計ネジおよびその製造方法 Download PDFInfo
- Publication number
- WO2016104329A1 WO2016104329A1 PCT/JP2015/085378 JP2015085378W WO2016104329A1 WO 2016104329 A1 WO2016104329 A1 WO 2016104329A1 JP 2015085378 W JP2015085378 W JP 2015085378W WO 2016104329 A1 WO2016104329 A1 WO 2016104329A1
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- WO
- WIPO (PCT)
- Prior art keywords
- screw
- oxide layer
- screw base
- base material
- manufacturing
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 25
- 239000010959 steel Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000005496 tempering Methods 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 abstract description 29
- 230000007797 corrosion Effects 0.000 abstract description 29
- 239000000758 substrate Substances 0.000 abstract description 10
- 239000010410 layer Substances 0.000 abstract 4
- 239000011247 coating layer Substances 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001315 Tool steel Inorganic materials 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
- C23C8/14—Oxidising of ferrous surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
- F16B33/00—Features common to bolt and nut
- F16B33/06—Surface treatment of parts furnished with screw-thread, e.g. for preventing seizure or fretting
Definitions
- the present invention relates to a watch screw.
- the watch screw of the present invention is a watch screw having a deep and dark interference film blue color that contributes to decorativeness and excellent scratch resistance and corrosion resistance.
- the present invention also relates to a method of manufacturing the timepiece screw described above. In particular, the manufacturing method of the present invention can easily mass-produce the watch screws.
- Blue is one of the most popular colors, and the blue color due to interference colors is preferred because it has a deep and deep luxury.
- Patent Document 1 discloses that an iron oxide layer is formed by heat-treating pure iron clock hands in the atmosphere at 300 to 450 ° C. for several tens of seconds to oxidize the surface of the substrate. It discloses that a (colored layer) is formed.
- Non-Patent Document 1 describes that the amount of CO and CO 2 gas generated increases as the amount of C in the substrate increases, and as a result, the void generation rate at the substrate interface increases.
- the present invention provides the following.
- a watch screw comprising a membrane.
- the timepiece screw according to claim 1 or 2 wherein the fluorine coating film has a thickness of 2 nm to 6 nm.
- a method for manufacturing the timepiece screw comprising: [6] The manufacturing method according to item [5], wherein the heating time is 6 hours or less.
- the present invention provides a timepiece screw having a deep and deep interference film blue color that contributes to decorativeness and excellent scratch resistance and corrosion resistance.
- the present invention provides a method for manufacturing the timepiece screw, particularly a method for easily mass-producing the timepiece screw.
- a timepiece screw according to the present invention comprises a screw base made of steel containing 0.5 to 1.0% by mass of carbon, an oxide layer of the steel having a thickness of 60 nm to 80 nm on the screw base, and the oxide layer An upper fluorine coating film.
- the timepiece screw according to the present invention must have a steel screw base containing 0.5 to 1.0% by mass of carbon.
- the screw base material refers to a steel material processed into a screw shape, and includes 0.5% by mass to 1.0% by mass of carbon.
- the hardness and tensile strength of the steel material are improved.
- Steel materials containing carbon can be further increased in surface hardness by quenching and tempering. If the carbon content is too small, the effect of improving hardness and strength is not sufficient, so the lower limit of the carbon content is 0.5% by mass. However, when there is too much carbon content, the toughness of steel materials may fall.
- the upper limit of the carbon content is 1.0% by mass.
- the screw base material including the carbon content in this range has sufficient strength and hardness and excellent scratch resistance.
- the size of the screw base material is not particularly limited. However, since it is a watch screw, the target screw diameter is generally 0.4 mm to 1.0 mm and the total screw length is 1.0 mm to 3.0 mm. It is good. As will be described later, the screw of the present invention has a fluorine coating film, and the scratch resistance is also improved by this fluorine coating film.
- the steel material is not particularly limited as long as it has the above-described carbon content, and in consideration of availability, workability, quenching / tempering property, etc., commercially available carbon tool steel or carburized steel may be used. Good.
- the surface hardness of the screw base material may be Vickers hardness (Hv; micro Vickers hardness meter, measured with 5 g load, holding time 10 seconds) 500 to 700. Since the screw base material contains carbon, it is possible to achieve a desired surface hardness by quenching and tempering. If it is less than Hv500, the strength as a practical screw is not sufficient.
- the upper limit of Hv is not particularly limited. However, when the Hv is increased with a steel material having a carbon content of 1.0% by mass or less, problems such as a decrease in toughness may occur. Therefore, the upper limit of Hv may be 700.
- the timepiece screw of the present invention must have an oxide layer having a thickness of 60 nm or more and 80 nm or less on the surface of the screw base.
- This oxide layer results in a deep and dark interference film blue color that contributes to decorativeness. Since this blue color includes a color realized by interference, if the thickness of the oxide layer is too thin or too thick, a desired blue color cannot be obtained.
- the thickness of the oxide layer is less than 60 nm, colors such as transparent, deep purple, and purple are provided, and when it exceeds 80 nm, colors such as purple, green, yellow, and red are provided. Therefore, the thickness of the oxide layer is set to 60 nm to 80 nm.
- the oxide layer can be obtained by heat-treating the screw base material in the atmosphere and oxidizing the surface of the screw base material. During this heat treatment, the carbon content in the screw base material is CO or CO 2. This is because the locations where carbon (C) has fallen off from the surface of the substrate become voids and become pinholes. If pinholes are present on the surface of the oxide layer, corrosion of the base material tends to proceed from the pinholes, resulting in poor corrosion resistance.
- the screw of the present invention includes a fluorine coating film on the oxide layer, and excellent corrosion resistance is ensured by this fluorine coating film.
- the oxide layer may have 10 or less pinholes having a surface opening diameter of 0.3 ⁇ m or more per 50 ⁇ m square surface area. If it is this range, the pinhole which exists in the surface of an oxide layer will be sufficiently few, it will become difficult to progress corrosion of a base material, and corrosion resistance will improve further.
- the oxide layer can be obtained by heat-treating the screw base material in the atmosphere and oxidizing the surface of the screw base material.
- the desired oxide can be obtained by heating the screw base material in the atmosphere at a temperature of 300 ° C. or lower for 30 minutes or more. It was found. If the temperature is 300 ° C. or higher, the oxidation proceeds too much and the thickness of the oxide layer becomes too thick, and the desired blue color cannot be obtained. It is conceivable to adjust the thickness of the oxide layer by shortening the heating time even at 300 ° C. or higher.
- Patent Document 1 a pure iron clock hand containing no carbon is heat-treated at 300 to 450 ° C.
- the heating temperature is not particularly limited as long as the oxide layer of the screw base material (steel material) can be formed, but if the heating temperature is too low, it takes time to form the oxide layer, and the productivity Therefore, 240 ° C. may be set as the lower limit. Moreover, since productivity falls even if heating time is too long, it is good also considering 6 hours as an upper limit. More preferably, the upper limit may be 4.5 hours.
- the thickness of the oxide layer is considered to have a positive correlation with the heating temperature and the heating time. That is, the higher the heating temperature, the thicker the oxide layer, and the longer the heating time, the thicker the oxide layer. Therefore, more appropriate heating conditions may be set by combining the heating temperature and the heating time.
- the screw base is too large or too small, changes in heating conditions (heat transfer conditions) and atmospheric conditions become large, and the thickness of the oxide layer may vary. If the screw base has a screw diameter of 0.4 mm to 1.0 mm and a total screw length of 1.0 mm to 3.0 mm, there is no significant change in heating conditions (heat transfer conditions) or atmospheric conditions, and the thickness of the oxide layer There is no variation in thickness and a uniform deep dark interference blue color is produced.
- This heating condition can also be applied to simultaneously processing 1000 or more screw base materials. Since it is heated for 30 minutes or more, it can provide uniform heating conditions for each of 1000 or more screw base materials, and there is no variation in the thickness of the oxide layer, and it is a uniform deep dark blue interference color Is brought about. With heating for several tens of seconds as in Patent Document 1, it is difficult to uniformly heat 1000 or more screw base materials simultaneously.
- the surface of the screw base may be washed before forming the oxide layer on the surface of the screw base.
- the screw base material may be rusted even when left in the air, and it is preferable to clean the surface of the screw base material in order to form a uniform oxide layer.
- the cleaning method is not particularly limited, and a general steel cleaning method can be used. Alkaline cleaning, acid cleaning, pure water rinse, alcohol cleaning, ultrasonic cleaning, and the like may be used, and they may be combined appropriately.
- the timepiece screw of the present invention must have a fluorine coating film on the surface of the oxide layer.
- the raw material of the fluorine coating film may include, but are not limited to, fluorine-based resins such as fluorinated polyolefin, polytetrafluoroethylene, polyvinylidene fluoride, and copolymers of these polymerizable substances. It is possible to uniformly coat the surface of the oxide layer with fluorine by dip-coating a liquid paint containing a fluorine-based resin on a screw base provided with an oxide layer and drying the paint. Since the surface of the oxide layer is coated with fluorine resin screws, excellent scratch resistance and corrosion resistance are realized.
- the fluorine coating film can be made sufficiently thin, and the deep and deep interference blue color due to the oxide layer is not impaired. Even with such a thin fluorine coating film, excellent scratch resistance and corrosion resistance can be exhibited.
- the thickness of the fluorine coating film is not particularly limited as long as it does not impair the deep and dark interference blue color and exhibits excellent scratch resistance and corrosion resistance, and may be 2 nm or more to 6 nm or less. If the thickness of the fluorine coating film is less than 2 nm, scratch resistance and corrosion resistance may be reduced, and if it exceeds 6 nm, the interference blue color due to the oxide layer may be affected.
- the oxide layer may have a pinhole as long as it does not affect the corrosion resistance, and the fluorine coating film penetrates into the pinhole to produce an anchor effect, so that the fluorine coating film is more strongly oxidized. It adheres to the layer and can further improve corrosion resistance and scratch resistance.
- one or more pinholes having a surface opening diameter of 0.3 ⁇ m or more may be present per 50 ⁇ m square surface area in the oxide layer.
- the corrosive action from the pinholes is accelerated, and excellent corrosion resistance and scratch resistance cannot be obtained even with the protective action by the fluorine coating film.
- the surface (oxide layer) of the screw base material Before the surface of the oxide layer is subjected to the fluorine coating treatment, the surface (oxide layer) of the screw base material may be washed.
- the fluorine coating is more easily dip-applied, resulting in a uniformly deep and dark interference blue color.
- a cleaning method a method of cleaning the screw base material before forming the oxide layer described above may be used, but a mild cleaning method is used so that a relatively thin oxide layer is not peeled off. It is preferable. You may ultrasonically wash in alcohol solutions, such as ethanol.
- SK95 (SK4) (JIS G 4401: 2006), which is a carbon tool steel material, is machined to obtain a screw base material (screw diameter 0.4 to 1.0 mm, total screw length 1.0 to 3.0 mm) ). Thereafter, quenching and tempering were performed to treat the hardness to Hv650. Before the heat treatment for obtaining the oxide layer (blue colored layer), the screw base material was washed. After the screw base material is prepared (after quenching and tempering), rust is generated even when left in the air, and the Fe 2 O 3 oxide film is unevenly formed on the surface of the screw base material. This is because it may be formed.
- the screw base material is immersed in an alkaline aqueous solution for 5 minutes, then rinsed with pure water for 5 minutes, then the pure water is replaced with ethanol, and then 100 ° C. or lower using an air suction type dryer. Suction drying at a temperature of 3 minutes or more. Heat treatment was performed to obtain a deep and dark interference film blue oxide layer.
- the heat treatment conditions are as shown in Table 1.
- the heat treatment of the screw base material was carried out in an atmospheric circulation type atmospheric furnace capable of simultaneous processing in units of thousands.
- the screw base with an oxide layer is ultrasonically cleaned in ethanol and dried, and then a fluororesin paint (Durasurf DS5210TH manufactured by Harves Co., Ltd.) is applied by dip coating. The surface of the physical layer was coated with fluorine.
- the timepiece screw of the present invention had a deep and dark interference film blue color that contributed to decorativeness, and was excellent in scratch resistance and corrosion resistance.
- FIG. 1 is an electron microscope image obtained by observing a pinhole of a timepiece screw according to the present invention.
- the heat treatment was performed at a higher temperature than in the present invention. By shortening the heat treatment, the oxide layer thickness was adjusted to obtain a deep dark interference film blue color. However, there were many pinholes.
- FIG. 2 is an electron microscope image obtained by observing a pinhole of a clock screw of a comparative example. For this reason, the corrosion resistance and scratch resistance were poor, and even with a fluorine coating film, only corrosion resistance and scratch resistance lower than those of the present invention were obtained.
- a watch screw produced under the same conditions as in the examples except that no fluorine coating was used was also evaluated. The corrosion resistance / scratch resistance of the watch screw of this reference example was superior to that of the comparative example, but inferior to that of the example.
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Abstract
Description
また、本発明は前記の時計ネジの製造方法に関係する。特に、本発明の製造方法は、前記時計ネジを容易に大量生産し得る。
[1] 炭素を0.5~1.0質量%含む鋼製のネジ基材、前記ネジ基材上の厚さ60nm~80nmの前記鋼の酸化物層、および前記酸化物層上のフッ素コーティング膜、を含んでなる、時計ネジ。
[2] 前記酸化物層が、50μm四方の表面積あたり、直径0.3μm以上のピンホールを10個以下有することを特徴とする、項目[1]に記載の時計ネジ。
[3] 前記フッ素コーティング膜の厚さが、2nm~6nmであることを特徴とする、請求項1または2に記載の時計ネジ。
[4] 前記ネジ基材の表面硬度がHv500~700であることを特徴とする、項目[1]~[3]のいずれか1項に記載の時計ネジ。
[5] 項目[1]~[4]のいずれかに記載の時計ネジの製造方法であって、
前記ネジ基材を用意する工程、
前記ネジ基材を大気雰囲気中で300℃以下の温度で30分以上加熱して、前記酸化物層を形成する工程、
前記酸化物層に前記フッ素コーティング膜を形成する工程、
を含んでなる、前記時計ネジの製造方法。
[6] 前記加熱時間が6時間以下であることを特徴とする、項目[5]に記載の製造方法。
[7] 前記加熱工程の前に、前記ネジ基材を焼き入れ焼き戻しする工程をさらに含んでなる、項目[5]または[6]に記載の製造方法。
[8] 前記加熱工程において、1000個以上の前記ネジ基材を同時に加熱することを特徴とする、項目[5]~[7]のいずれか1項に記載の製造方法。
なお、本発明のネジは、後述するとおり、フッ素コーティング膜を有しており、このフッ素コーティング膜によっても耐傷性が向上している。
耐食性をさらに高めるために、酸化物層において、50μm四方の表面積あたり、表面開口部の直径が0.3μm以上のピンホールが10個以下としてもよい。この範囲であれば、酸化物層の表面に存在するピンホールは十分に少なく、基材の腐食がより進行しにくくなり、耐食性はさらに向上する。
また加熱時間が長すぎても、生産性が低下するので、6時間を上限としてもよい。さらに好ましくは、4.5時間を上限としてもよい。
また酸化物層の厚みは、加熱温度、加熱時間と正の相関を有すると考えられる。つまり、加熱温度が高いほど酸化物層は厚くなり、また加熱時間が長いほど酸化物層は厚くなると考えられる。したがって、加熱温度と加熱時間とを組み合わせて、より適当な加熱条件を設定してもよい。ネジ基材が極端に大きすぎたり、小さすぎたりすると、加熱条件(伝熱条件)や雰囲気条件の変化が大きくなり、酸化物層の厚さにバラツキを生じるおそれがある。ネジ径が0.4mm~1.0mm、ネジ全長が1.0mm~3.0mmのネジ基材であれば、加熱条件(伝熱条件)や雰囲気条件の大きな変化はなく、酸化物層の厚さにバラツキを生じることがなく、均一な深く濃い干渉ブルー色がもたらされる。
酸化物層(ブルー色着色層)を得るための加熱処理の前に、ネジ基材の洗浄を行った。ネジ基材を用意した後(焼き入れ焼き戻しを行った後)、空気中に放置している間も錆びが発生し、ネジ基材の表面にはFe2O3の酸化膜が不均一に形成されていることもあるからである。具体的には、ネジ基材をアルカリ水溶液に5分間浸漬し、次に純水で5分間リンスし、次に純水をエタノールに置換し、その後大気吸引式の乾燥機を用いて100℃以下の温度で3分以上吸引乾燥した。
深く濃い干渉膜ブルー色の酸化物層を得るための加熱処理を行った。加熱処理条件は表1に示したとおりである。ネジ基材の加熱処理は、数千個単位で同時処理可能な大気循環式の大気炉内で実施した。
酸化物層を備えたネジ基材を、エタノール中で超音波洗浄し乾燥させた後、フッ素樹脂塗料((株)ハーベス社製 DURASURF DS5210TH)を浸漬塗布し、この塗料を乾燥することにより、酸化物層の表面にフッ素コーティングした。
(1)表面ピンホールの観察:時計ネジの表面に存在するピンホールを、走査型電子顕微鏡(倍率×1000)を用いて観察した。「○」は、50μm四方の表面積あたり、表面開口部の直径が0.3μm以上のピンホールが10個以下である。「×」は、ピンホールが10個超のものである。
(2)耐食性:時計ネジを温度40 ℃、湿度90% RHの環境下において、所定時間後に錆が発生しているかどうかを目視で確認する。「○」は、錆が発生しなかったものである。「×」は、24時間後に錆が発生したものである。「△」は、1週間後には錆が確認されたものである。
(3)耐傷性:時計自動組立では、手作業による組立よりも多少乱暴に取り扱われる。得られた時計ネジの耐傷性を評価するために、時計自動組立ラインの振動パーツフィーダーに時計ネジを投入し、その後時計ネジの表面の疵を目視観察した。「○」は、傷が発生しなかったものである。「×」は、目視で確認できる傷が発生したものである。「△」は、倍率10倍の双眼顕微鏡で確認できる傷が発生したものである。
(4)総合評価:ピンホールの有無、耐食性、耐傷性に関して、すべてが「○」であれば、総合評価「○」とした。すべてが「×」であれば、総合評価「×」とした。それ以外を総合評価「△」とした。
比較例は、本発明に比べて高温で加熱処理を行っており、その分短めにすることにより、酸化物層厚さを調節して深く濃い干渉膜ブルー色を得た。しかし、ピンホールが多かった。図2は、比較例の時計ネジのピンホールを観察した電子顕微鏡画像である。そのため、耐食性・耐傷性が悪く、フッ素コーティング膜があっても、本発明よりも低い耐食性・耐傷性しか得られなかった。
なお、参考のために、フッ素コートをしないこと以外は、実施例と同じ条件で作製した時計ネジについても評価した。この参考例の時計ネジの耐食性・耐傷性は、比較例よりは優れていたが、実施例よりは劣るものが見られた。
Claims (8)
- 炭素を0.5~1.0質量%含む鋼製のネジ基材、前記ネジ基材上の厚さ60nm~80nmの前記鋼の酸化物層、および前記酸化物層上のフッ素コーティング膜、を含んでなる、時計ネジ。
- 前記酸化物層が、50μm四方の表面積あたり、直径0.3μm以上のピンホールを10個以下有することを特徴とする、請求項1に記載の時計ネジ。
- 前記フッ素コーティング膜の厚さが、2nm~6nmであることを特徴とする、請求項1または2に記載の時計ネジ。
- 前記ネジ基材の表面硬度がHv500~700であることを特徴とする、請求項1~3のいずれか1項に記載の時計ネジ。
- 請求項1~請求項4のいずれか1項に記載の時計ネジの製造方法であって、
前記ネジ基材を用意する工程、
前記ネジ基材を大気雰囲気中で300℃以下の温度で30分以上加熱して、前記酸化物層を形成する工程、
前記酸化物層に前記フッ素コーティング膜を形成する工程、
を含んでなる、前記時計ネジの製造方法。 - 前記加熱時間が6時間以下であることを特徴とする、請求項5に記載の製造方法。
- 前記加熱工程の前に、前記ネジ基材を焼き入れ焼き戻しする工程をさらに含んでなる、請求項5または請求項6に記載の製造方法。
- 前記加熱工程において、1000個以上の前記ネジ基材を同時に加熱することを特徴とする、請求項5~7のいずれか1項に記載の製造方法。
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