WO2024252634A1 - ファスナー部品 - Google Patents
ファスナー部品 Download PDFInfo
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- WO2024252634A1 WO2024252634A1 PCT/JP2023/021417 JP2023021417W WO2024252634A1 WO 2024252634 A1 WO2024252634 A1 WO 2024252634A1 JP 2023021417 W JP2023021417 W JP 2023021417W WO 2024252634 A1 WO2024252634 A1 WO 2024252634A1
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- fastener
- base material
- oxide coating
- fastener part
- mass
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/42—Making by processes not fully provided for in one other class, e.g. B21D53/50, B21F45/18, B22D17/16, B29D5/00
Definitions
- the present invention relates to a fastener part. More specifically, the present invention relates to a fastener part having a base material of pure zinc or a zinc alloy.
- Fastener products such as slide fasteners and buttons are often made up of multiple parts (hereinafter also referred to as "fastener parts").
- Some fastener parts use pure zinc or zinc alloy as the base material.
- Such fastener parts made of pure zinc or zinc alloy are often plated to improve corrosion resistance and also to change the color tone.
- Copper plating has often been used to improve corrosion resistance.
- plating Ni plating, Cu-Sn-Zn alloy plating, etc.
- plating has often been used to give the color a silver color that gives a sense of weight and luxury. For this reason, copper plating is applied to the surface of pure zinc or zinc alloy, which is originally silver-colored, and then further plating is applied to restore the silver color.
- plating requires special chemicals and places a large burden on the environment, including waste liquid treatment.
- fastener parts are plated with multiple layers of different types of plating, in order to recycle fastener parts made of plated pure zinc or zinc alloy as a base material, it is necessary to remove elements derived from the plating components, which increases costs. For this reason, from the perspective of the SDGs, there has been a recent demand for fastener parts that have a small environmental burden during waste liquid treatment, are highly recyclable, and have practical corrosion resistance.
- Patent Document 1 discloses that for fastening parts such as sliders, clampers, pull tabs, top and bottom stoppers, separable inserts, and elements (teeth) of slide fasteners, as well as accessories such as buttons, buckles, belts, pendants, and accessories (tie pins, hat pins, bracelets, earrings, watch chains, etc.), a nickel-like appearance can be achieved without nickel plating by chromating the surface of a base material made of pure zinc or a pure zinc layer formed on the base material, and then coating it with a brown-colored clear coating layer.
- Patent Document 1 a nickel-like appearance is obtained by chromate treatment and a brown-colored clear coating layer without plating. Therefore, the technology described in Patent Document 1 can reduce the environmental load during wastewater treatment.
- restrictions on the use of harmful substances such as hexavalent chromium, which is a type of chromate treatment have been promoted in order to further reduce the environmental load.
- chromate treatment has a smaller environmental load than plating, it is still not sufficient.
- the surface of a substrate made of pure zinc or a pure zinc layer formed on the substrate is chromate treated and then covered with a brown-colored clear coating layer, so a coating layer with a different color tone from the substrate is formed.
- Patent Document 1 targets pure zinc as the substrate, considering the application to die casting, which is often used as a method for manufacturing fastener parts, it is desirable to provide a technology that can be applied not only to pure zinc but also to zinc alloys.
- Patent Document 1 also describes a die-cast product that uses a zinc alloy substrate containing about 4% Al, but in this case, Cu plating and Zn-Cu alloy plating are performed, so the environmental impact cannot be reduced.
- the present invention was created in consideration of the above circumstances, and in one embodiment, it is an object of the present invention to provide a fastener component whose base material is pure zinc or a zinc alloy, which has practical corrosion resistance, has a small environmental impact, and is easy to recycle. In another embodiment, it is another object of the present invention to provide a fastener product that includes such a fastener component.
- the inventors conducted extensive research to solve the above problems and discovered that it is effective to form a coating containing zirconium oxide on the surface of a fastener part whose base material is pure zinc or a zinc alloy, leading to the creation of the present invention, which is exemplified below.
- a fastener component comprising a base material made of pure zinc or a zinc alloy and a zirconium oxide coating covering at least a portion of the surface of the base material.
- the color tone of the surface of the oxide coating is expressed in the Lab color system, and is within the ranges of L * of 50 to 80, a * of -10 to 10, and b * of -15 to 15.
- the fastener part according to any one of [1] to [3].
- fastener part according to any one of [1] to [10], wherein the fastener part is an element of a slide fastener, and has a rating number of 2 or more when a reciprocating opening/closing durability test measured according to JIS S3015:2019 is conducted and then a neutral salt spray test measured according to JIS Z2371:2015 is conducted.
- fastener part according to any one of [1] to [10], wherein the fastener part is a bottom stop of a slide fastener, and has a rating number of 2 or more when a neutral salt spray test measured according to JIS Z2371:2015 is carried out after the fastener part is crimped and fixed to a fastener tape.
- fastener part according to any one of [1] to [10], wherein the fastener part is a button cap and has a rating number of 2 or more when a neutral salt spray test measured in accordance with JIS Z2371:2015 is carried out.
- a fastener product comprising the fastener part according to any one of [1] to [15].
- the fastener part according to one embodiment of the present invention does not have a plating layer, but instead has a zirconium oxide coating.
- the zirconium oxide coating has high corrosion resistance, so that practical corrosion resistance can be obtained for fastener parts made of pure zinc or zinc alloy as a base material.
- the zirconium oxide coating is nearly colorless and transparent, and can almost maintain the color tone of the base material.
- the typical Cu-Sn-Zn plating for producing a silver color contains tin, which causes grain boundary corrosion of zinc and makes recycling of fastener parts difficult, but the fastener part does not contain tin. For these reasons, the fastener part is easy to recycle.
- the zirconium oxide coating can be formed by a non-chromium chemical conversion treatment, and has a smaller environmental impact than plating treatment or chromate treatment. Therefore, according to one embodiment of the present invention, it is possible to provide an excellent fastener part from the perspective of the SDGs.
- FIG. 2 is a schematic plan view of a slide fastener.
- 5A to 5C are schematic diagrams illustrating a method of attaching a bottom end stop, a top end stop, and an element to a fastener tape.
- FIG. 2 is a schematic side view of a button cap.
- 1 is an example of a cross-sectional photograph of a zirconium oxide coating including the boundary with the base material for a fastener part (slider) of Example 2.
- fastener parts The fastener parts covered by the present invention are not particularly limited as long as they are fastener product parts, but representative examples include slide fastener parts and button parts.
- Slide fastener parts include sliders, elements, top stops, bottom stops, and pull tabs.
- Button parts include caps and bodies. These parts may be provided as pressed products, but are preferably provided as die-cast products that mainly use pure zinc or zinc alloys.
- the present invention is particularly suitable for use with die-cast sliders.
- FIG. 1 is a schematic plan view of a slide fastener.
- the slide fastener comprises a pair of fastener tapes 1 each having a core 2 formed along one side edge, a row of elements 3 fixed (attached) at a predetermined interval to the core 2 of the fastener tape 1, an upper stop 4 and a lower stop 5 fixed to the core 2 of the fastener tape 1 by crimping at the upper and lower ends of the row of elements 3, and a slider 6 arranged between the pair of opposing rows of elements 3 and capable of sliding in the vertical direction for engaging and separating the rows of elements 3.
- At least a part of the components constituting the slide fastener can be constituted by the fastener components according to the embodiment of the present invention.
- a row of elements 3 attached to the core 2 of one fastener tape 1 is called a slide fastener stringer
- a row of elements 3 attached to the core 2 of a pair of fastener tapes 1 in an engaged state is called a slide fastener chain 7.
- the slider 6 shown in FIG. 1 comprises a slider body 61 and a pull tab 62 attached to the slider body 61.
- the slider body 61 can be produced by die-casting pure zinc or a zinc alloy.
- the slider body 61 may also be produced by pressing a long body made of a plate with a rectangular cross section in multiple stages and cutting it at predetermined intervals.
- the pull tab can be punched out into a predetermined shape from a plate with a rectangular cross section, for example, and then secured to the slider body by crimping.
- the pull tab 62 may be provided as a die-cast product made of pure zinc or a zinc alloy.
- Figure 2 is a schematic diagram showing a manufacturing method for the element 3, top stop 4, and bottom stop 5 of the slide fastener shown in Figure 1, and how to attach them to the core 2 of the fastener tape 1.
- the element 3 is formed by cutting a deformed wire 8 having a roughly Y-shaped cross section to a predetermined size and press-molding it to form an engaging head 9, and then fixing it to the core 2 of the fastener tape 1 by crimping both legs 10.
- the element 3 may be provided as a die-cast product made of pure zinc or a zinc alloy, in which case the element 3 can be directly injection molded into the fastener tape 1.
- the top stop 4 is fixed by, for example, cutting a rectangular wire 11 (rectangular wire) having a rectangular cross section to a predetermined size, bending it to form an approximately U-shaped cross section, and then crimping it to the core 2 of the fastener tape 1.
- the bottom stop 5 is fixed by, for example, cutting a deformed wire 12 having an approximately X-shaped cross section to a predetermined size, and then crimping it to the core 2 of the fastener tape 1.
- the top stop 4 and/or the bottom stop 5 may be provided as a die-cast product made of pure zinc or a zinc alloy, in which case the top stop 4 and/or the bottom stop 5 can be directly injection molded into the fastener tape 1.
- the bottom stop 5 may also be a separable insert consisting of a butterfly pin, a box pin, and a box body, and may be one that allows the pair of slide fastener chains 7 to be separated by opening the slider.
- buttons include tack buttons and snap buttons.
- Tack buttons generally have a button body and a button fastener, and are used on jeans, etc.
- Snap buttons generally have a stud and a socket that can be connected and disconnected from each other, and may have a cap attached for decorative purposes.
- Figure 3 shows an example side view of a cap with a snap button as a fastener part.
- the cap 30 shown in Figure 3 comprises a disk-shaped top plate 31 and a peripheral side plate 32 that serves as a peripheral side portion extending from the radially outer end of the top plate 31 to the back side.
- the surface of the top plate 31 is flat or a curved surface that is slightly convex toward the front side (upward in the paper surface of Figure 3).
- the dotted line indicates the outline of the back surface of the cap.
- the fastener component according to one embodiment of the present invention has practical corrosion resistance.
- the fastener part is a slider body of a slide fastener
- the slider body can be subjected to a reciprocating opening/closing durability test measured in accordance with JIS S3015:2019 and then a neutral salt spray test measured in accordance with JIS Z2371:2015, resulting in a rating number of 2 or higher.
- the fastener component is an element of a slide fastener
- the element can have a rating number of 2 or higher when subjected to a reciprocating opening/closing durability test measured in accordance with JIS S3015:2019 and then a neutral salt spray test measured in accordance with JIS Z2371:2015.
- the rating number can be 2 or higher when a neutral salt spray test measured in accordance with JIS Z2371:2015 is carried out.
- the fastener part when the fastener part is a button cap, the fastener part may have a rating number of 2 or more when a neutral salt spray test measured in accordance with JIS Z2371:2015 is carried out.
- Fasteners such as slide fasteners and buttons can be attached to various articles, and in particular function as opening and closing devices.
- articles to which fasteners can be attached include everyday items such as clothing, footwear, bags, bedding, and outdoor equipment, as well as industrial items such as water tanks, fishing nets, and space suits.
- the base material is pure zinc or a zinc alloy.
- the base material has a composition that contains 0 to 4.3 mass% Al, 0 to 1.25 mass% Cu, 0 to 0.06 mass% Mg, 0 to 0.10 mass% Fe, and the balance is Zn and unavoidable impurities. This composition includes both pure zinc and zinc alloys.
- pure zinc refers to zinc having a composition consisting of Zn and unavoidable impurities and a purity of 99.7% by mass or more.
- pure zinc having a composition corresponding to the highest purity zinc bullion, special zinc bullion, ordinary zinc bullion, or special distilled zinc bullion as specified in JIS H2107:2015 can be used.
- the base material contains 3.5 to 4.3 mass% Al, 0.75 to 1.25 mass% Cu, 0.02 to 0.06 mass% Mg, 0 to 0.10 mass% Fe, with the balance being Zn and unavoidable impurities.
- a zinc alloy having a composition corresponding to zinc alloy die-casting type 1 (ZDC1) or zinc alloy die-casting type 2 (ZDC2) as specified in JIS H5301:1990 can be suitably used.
- Inevitable impurities are impurities that are present in raw materials or that are inevitably mixed in during the manufacturing process. They are essentially unnecessary, but are tolerated because they are present in trace amounts and do not affect the properties.
- the content of each impurity element tolerated as an unavoidable impurity is generally 0.1% by mass or less, and preferably 0.05% by mass or less.
- a zirconium oxide coating is provided that covers at least a portion of the surface of the base material.
- the zirconium oxide coating contains ZrO2 .
- the zirconium oxide coating can cover 60% or more of the surface area of the base material, can cover 80% or more, can cover 95% or more, or can cover the entire surface area.
- the zirconium oxide coating is highly practical because it can provide excellent corrosion resistance.
- the zirconium oxide coating floats on the surface of the molten metal during recycling, making it easy to remove. Even if it does get mixed into the base material, it does not change color, making it suitable for recycling.
- Another advantage is that the color tone of the base material is utilized, so there is little discomfort in appearance even if the oxide coating peels off during use.
- the zirconium oxide coating can be formed by a non-chromium chemical conversion treatment, which places less of a burden on the environment than plating or chromate treatments.
- the interference color can be controlled, and the color tone can be adjusted. Therefore, by adjusting the thickness, it is possible to make the color tone closer to that of the base material.
- the lower limit of the average thickness of the zirconium oxide coating is preferably 30 nm or more, and more preferably 60 nm or more.
- the upper limit of the average thickness of the zirconium oxide coating is preferably 150 nm or less, and more preferably 110 nm or less. Therefore, the average thickness of the zirconium oxide coating is preferably, for example, 30 to 150 nm, and more preferably 60 to 110 nm.
- the average thickness of the zirconium oxide coating is measured by the following method. First, a cross section perpendicular to the surface of the zirconium oxide coating is cut out from a flat portion of the fastener part to be measured (the part closest to flat if there is no flat portion) by the cross-section polisher (CP) method, and the cross section of the zirconium oxide coating including the boundary with the base material is observed in 10 arbitrary fields of view at 100,000 times magnification with a scanning electron microscope (SEM) (the area of one field of view is 0.90 ⁇ m vertical ⁇ 1.27 ⁇ m horizontal so that the vertical direction is the thickness direction of the coating).
- SEM scanning electron microscope
- Figure 4 shows an example of a cross-sectional photograph of the zirconium oxide coating 120 including the boundary with the base material 110 for the fastener part (slider) according to Example 2 described later.
- the thickness (T) of the zirconium oxide coating 120 near the center in the horizontal direction is measured at one point. This is performed for 10 fields of view, and the average thickness of the zirconium oxide coating 120 is calculated. This average value is the average thickness of the zirconium oxide coating on the fastener part.
- the color tone of the surface of the zirconium oxide coating can be expressed in the Lab color system as follows: L * is 50 to 80, a * is -10 to 10, and b * is -15 to 15.
- L * is 50 to 80, a * is -10 to 1, and b * is -12 to 3, and more preferably, L * is 50 to 78, a * is -9 to 0, and b * is -12 to 0.
- the "color tone of the surface of the zirconium oxide coating" refers to the color tone measured when the exposed surface of the zirconium oxide coating is color-measured, and does not necessarily mean the color tone of the zirconium oxide coating itself. When the zirconium oxide coating is transparent, the color tone reflects the color tone of the base material inside the oxide coating.
- the color tone of the surface of the zirconium oxide coating is similar to that of the surface of the base material.
- the color difference ⁇ E * ab between the surface of the base material and the surface of the zirconium oxide coating in the Lab color system is preferably 20 or less, more preferably 17 or less, and even more preferably 15 or less.
- the color difference ⁇ E * ab is typically 0 to 15, and more typically 8 to 15.
- the Lab color system refers to the CIE1976L * a * b * color space defined in JIS Z8781-4:2013.
- the color tone of the surface of the zirconium oxide coating is given as the average value of the color values measured at 10 arbitrary points on the flat portion (the portion closest to flat if there is no flat portion) on the fastener part to be measured, using a color difference meter.
- the color measurements are performed in accordance with the specifications of the color difference meter under the conditions of a dome-shaped LED light source (color temperature 8500K), a color measurement area of 0.5 mm2 per point, a temperature of 15 to 30°C, and a humidity of 30 to 75% RH.
- the color tone of the surface of the base material is given as the average value of the color values measured at 10 arbitrary points on a flat portion of the base material before the oxide film is formed (or the portion closest to flat if there is no flat portion).
- the color measurements are performed in accordance with the specifications of the color difference meter using a dome-shaped LED light source (color temperature 8500K) with a color measurement area of 0.5 mm2 per point, at a temperature of 15 to 30°C and a humidity of 30 to 75% RH.
- a transparent resin layer may be further provided to cover at least a part of the surface of the oxide coating.
- the transparent resin layer may be formed for the purpose of further adjusting the color tone. From the viewpoint of imparting a uniform color tone, the transparent resin layer may cover 60% or more of the surface area of the oxide coating, may cover 80% or more, may cover 95% or more, or may cover the entire surface area.
- the transparent resin layer By adjusting the thickness of the transparent resin layer, the interference color can be controlled, and the color tone can be adjusted. Therefore, by adjusting the thickness, it is possible to make the color tone closer to that of the base material.
- the transparent resin layer preferably has a lower limit of the average thickness of 0.5 ⁇ m or more, more preferably 0.6 ⁇ m or more, and even more preferably 0.8 ⁇ m or more.
- the transparent resin layer preferably has an upper limit of the average thickness of 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less. Therefore, the average thickness of the transparent resin layer is, for example, preferably 0.5 to 30 ⁇ m, more preferably 0.6 to 20 ⁇ m, and even more preferably 0.8 to 10 ⁇ m.
- the average thickness of the transparent resin layer is measured by the following procedure. First, a cross section perpendicular to the surface of the transparent resin layer is cut out from a flat portion of the fastener part to be measured (the part closest to flat if there is no flat portion) using a cross-section polisher (CP) method, and the cross section of the transparent resin layer including the boundary with the zirconium oxide coating is observed at 9,000 times magnification using a scanning electron microscope (SEM) in any 10 fields of view (the area of one field of view is 9.8 ⁇ m vertical ⁇ 14.0 ⁇ m horizontal, with the vertical direction being the thickness direction of the transparent resin layer). On the SEM photograph, the thickness of the transparent resin layer near the center in the horizontal direction is measured at one point. This is performed for 10 fields of view, and the average thickness of the transparent resin layer is calculated. This average value is the average thickness of the transparent resin layer in the fastener part.
- SEM scanning electron microscope
- the color tone of the surface of the transparent resin layer can be expressed in the Lab color system as follows: L * is 55 to 85, a * is -4 to 2, and b * is -3 to 6.
- L * is 55 to 80, a * is -4 to 1, and b * is -2 to 4, and more preferably, L * is 55 to 75, a * is -4 to 0, and b * is -2 to 2.
- the "color tone of the surface of the transparent resin layer” refers to the color tone measured when the exposed surface of the transparent resin layer is color-measured, and does not necessarily mean the color tone of the transparent resin layer itself.
- the color tone reflects the color tone of the zirconium oxide coating and the base material inside the transparent resin layer.
- the material constituting the transparent resin layer is not particularly limited as long as it is a resin used in general clear paints, but it may contain transparent resins such as acrylic resin, polyester resin, alkyd resin, urethane resin, silicone resin, fluororesin, and epoxy resin, either alone or in combination. Among these, epoxy resin is preferred from the viewpoint of adhesion.
- the transparent resin layer may appropriately contain a crosslinking agent such as blocked polyisocyanate, melamine resin, and urea resin.
- the transparent resin layer may contain additives such as a wetting dispersant, anti-settling agent, defoamer, and leveling agent.
- the color tone of the surface of the transparent resin layer is preferably similar to the color tone of the surface of the base material.
- the color difference ⁇ E * ab between the surface of the base material and the surface of the transparent resin layer in the Lab color system is preferably 15 or less, more preferably 12 or less, even more preferably 10 or less, and even more preferably 8 or less.
- the lower limit of the color difference ⁇ E * ab is not particularly set, and it is preferable to set it to 0, but some color difference may occur. Therefore, the color difference ⁇ E * ab is typically 3 to 10, more typically 4 to 8, and even more typically 5 to 7.
- the color tone of the surface of the transparent resin layer is given as the average value of the color of 10 arbitrary points of the flat portion (the portion closest to flat if there is no flat portion) on which the transparent resin layer is formed in the fastener part to be measured, measured with a color difference meter.
- the color measurement is performed in accordance with the specifications of the color difference meter under the conditions of a dome-shaped LED light source (color temperature 8500K), a color measurement area of 0.5 mm2 per point, a temperature of 15 to 30°C, and a humidity of 30 to 75% RH.
- Method for forming oxide film An example of a method for forming a zirconium oxide coating on the surface of the base material of the fastener component is chemical conversion treatment.
- the chemical conversion treatment can be carried out, for example, in the following order: degreasing step ⁇ water washing step ⁇ chemical conversion treatment step ⁇ water washing step ⁇ drying step.
- the chemical conversion treatment may be carried out repeatedly as necessary.
- the degreasing process and water washing process before the chemical conversion treatment process may be carried out according to conventional methods, and there are no particular limitations.
- the degreasing process can be carried out by alkaline degreasing.
- a known zirconium-based chemical conversion treatment liquid can be used.
- the zirconium-based chemical conversion treatment liquid that can be used include an aqueous solution of hexafluorozirconate (IV), an aqueous solution of zirconium nitrate, and an aqueous solution of ammonium zirconate fluoride.
- the chemical conversion treatment step can be performed by contacting the zirconium-based chemical conversion treatment liquid with the base material surface of the fastener part, but from the viewpoint of uniformly covering the entire base material surface, it is preferable to perform the chemical conversion treatment while immersing the fastener part in the zirconium-based chemical conversion treatment liquid.
- the chemical conversion treatment step is preferably performed by heating the zirconium-based chemical conversion treatment liquid to 40 to 50°C.
- the zirconium concentration of the zirconium-based chemical conversion treatment liquid is 0.3 to 0.5 g/L. The longer the time for which the chemical conversion treatment step is performed, the thicker the zirconium oxide film will be, so it is sufficient to adjust the time to obtain the desired thickness.
- the chemical conversion treatment process can be carried out for 2 to 60 minutes.
- the water washing and drying steps following the chemical conversion treatment step may be carried out according to standard methods, with no particular restrictions.
- the drying step is preferably carried out by blowing hot air at 80 to 120°C for 600 to 900 seconds. After carrying out the drying step, it is preferable to allow the workpiece to cool naturally without blowing cold air on it, in order to prevent cracking of the oxide coating.
- Method for forming transparent resin layer As a method for forming a transparent resin layer that covers at least a part of the surface of the zirconium oxide coating, a method of coating a clear coating on the surface of the zirconium oxide coating can be mentioned.
- the coating of the clear coating can be carried out, for example, in the order of a coating step ⁇ a preliminary drying (setting) step ⁇ a drying step.
- the coating of the clear coating can be carried out repeatedly as necessary.
- the clear paint can be used after diluting it appropriately with thinner.
- the diluted clear paint can be applied by contacting it with a fastener part having a zirconium oxide coating.
- Examples of application methods include the rotary barrel spray method and the dip coating method.
- the rotary barrel spray method is preferred because it is suitable for mass production of fastener parts.
- the rotary barrel spray method is a method in which the object to be coated is placed in a rotatable barrel and the paint is sprayed with a spray gun while rotating the object.
- the preliminary drying (setting) process is preferably performed by spraying hot air at 90 to 95°C for 150 to 180 seconds.
- the drying process is preferably performed by spraying hot air at 130 to 140°C for 810 to 900 seconds. After the drying process, it is preferable to allow the transparent resin layer to cool naturally without blowing cold air in order to prevent cracks.
- Example 1 A slider body (Model 5MDA81 manufactured by YKK Corporation) was manufactured by die casting using zinc alloy die casting type 1 (ZDC1) specified in JIS H5301:1990 as a raw material.
- ZDC1 zinc alloy die casting type 1
- the chemical conversion treatment was performed by immersing the slider body in a zirconium-based chemical conversion treatment solution (zirconium concentration: 0.4 g/L) heated to 50 ° C for the time listed in Table 1.
- the slider body was washed with water and dried by blowing hot air at 120 ° C for 15 minutes. Then, it was air-cooled at room temperature. As a result, a slider body in which the entire surface of the base material was covered with a zirconium oxide film was produced. The number of slider bodies required for the following tests was produced. It was confirmed by X-ray photoelectron spectroscopy (XPS) that the main component of the oxide film was ZrO 2 .
- XPS X-ray photoelectron spectroscopy
- Example 2 A slider body in which the entire surface of the base material was covered with a zirconium oxide film was produced in the same manner as in Example 1, except that the immersion time of the slider body in the chemical conversion treatment was changed to the time shown in Table 1. The number of slider bodies required for the following tests was produced.
- Example 4 A slider body was produced in which the entire surface of the base material was covered with a zirconium oxide coating in the same manner as in Example 1.
- a commercially available clear paint containing an epoxy resin product name EU Paint Clear, manufactured by Kansai Paint Co., Ltd.
- the diluted clear paint (about 22°C) was applied to the entire surface of the slider body for 2 minutes using a rotary barrel spray method.
- the slider body after the clear paint was applied was pre-dried by blowing hot air at 90°C for 2.5 minutes, and then dried by blowing hot air at 130°C for 15 minutes. Then, it was air-cooled at room temperature. In this way, a slider body was produced in which the entire surface of the zirconium oxide coating was covered with a transparent resin layer. The number of slider bodies required for the following tests was produced.
- Example 5 A slider body was produced in which the entire surface of the base material was covered with a zirconium oxide coating in the same manner as in Example 2. Next, a clear coating was applied to the slider body in the same manner as in Example 4, producing a slider body in which the entire surface of the zirconium oxide coating was covered with a transparent resin layer. The number of slider bodies required for the following tests was produced.
- Example 6 A slider body was produced in which the entire surface of the base material was covered with a zirconium oxide coating in the same manner as in Example 3. Next, a clear coating was applied to the slider body in the same manner as in Example 4, producing a slider body in which the entire surface of the zirconium oxide coating was covered with a transparent resin layer. The number of slider bodies required for the following tests was produced.
- Example 1 The slider body produced in Example 1 was degreased with alkali and washed with water, and then surface-conditioned with a commercially available zinc phosphate surface conditioner (Surf Fine GL1, manufactured by Nippon Paint Surf Chemicals Co., Ltd.). The surface conditioning was performed by immersing the slider body in a surface conditioning liquid adjusted to 25°C for 30 seconds. Next, chemical conversion treatment was performed using a commercially available chemical conversion treatment liquid containing zinc phosphate (Surf Dyne EC1000, manufactured by Nippon Paint Surf Chemicals Co., Ltd.). The chemical conversion treatment was performed by immersing the slider body in a zinc phosphate-based chemical conversion treatment liquid adjusted to 50°C for 100 seconds.
- a commercially available zinc phosphate surface conditioner Surf Fine GL1, manufactured by Nippon Paint Surf Chemicals Co., Ltd.
- the surface conditioning was performed by immersing the slider body in a surface conditioning liquid adjusted to 25°C for 30 seconds.
- chemical conversion treatment was performed using a commercially available chemical conversion treatment
- the slider body was washed with water and dried by blowing hot air at 60°C for 20 minutes. Then, the slider body was air-cooled at room temperature. As a result, a slider body was produced in which the entire surface of the base material was covered with a zinc phosphate coating. The slider body was produced in the number required for the following tests.
- Example 2 The slider body produced in Example 1 was degreased with an alkali and washed with water, and then chemically treated using a trivalent chromium-based chemical conversion treatment solution containing chromium nitrate, cobalt nitrate, inorganic acid, and a silicon compound.
- the chemical conversion treatment was performed by immersing the slider body in the trivalent chromium-based chemical conversion treatment solution adjusted to 25°C for 60 seconds. After the chemical conversion treatment, the slider body was washed with water and dried by blowing hot air at 60°C for 20 minutes. Then, it was air-cooled at room temperature. This produced a slider body in which the entire surface of the base material was covered with a trivalent chromium coating. The number of slider bodies required for the following tests was produced.
- the color measurement conditions were a color measurement area of 0.5 mm 2 per location, a temperature of 15 to 30° C., and a humidity of 30 to 75% RH.
- a dome-shaped LED light (color temperature 8500 K) was used as the light source.
- the color tone of the surface of the zirconium oxide coating was measured, and in Examples 4 to 6, the color tone of the surface of the transparent resin layer was measured.
- Comparative Example 1 the color tone of the zinc phosphate coating surface was measured, and in Comparative Example 2, the color tone of the trivalent chromium surface was measured.
- the surface of the base material was measured in the same manner before chemical conversion treatment. The results are shown in Table 1.
- a * and b * represent color tone
- a * represents a magenta-green color tone (+ is closer to magenta, - is closer to green)
- b * represents a yellow-blue color tone (+ is closer to yellow, - is closer to blue
- L * represents lightness, and the higher the value, the higher the gloss.
- Thickness of oxide coating and transparent resin layer The flat surface of the back center of the slider body of Examples 1 to 6 was cut in the thickness direction of the oxide film (and the transparent resin layer) to expose the cross section, and the average thickness of the zirconium oxide film and the average thickness of the transparent resin layer were measured by the method described above.
- the cutting of the slider body to expose the cross section of the zirconium oxide film (and the transparent resin layer) was performed by embedding the zirconium oxide film (and the transparent resin layer) in resin, mechanically polishing the zirconium oxide film (and the transparent resin layer), and then performing cross-section polishing (CP processing).
- the cross section of the zirconium oxide film (and the transparent resin layer) was observed using a scanning electron microscope (SEM) (Model S-4800 manufactured by Hitachi High-Tech Corporation) at a pressure voltage of 2 kV, a probe current of 80 ⁇ A, and a working distance (WD) of about 4 mm. The results are shown in Table 1.
- SEM scanning electron microscope
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
純亜鉛又は亜鉛合金製の母材と、当該母材の表面の少なくとも一部を被覆するジルコニウムの酸化物被膜とを備えたファスナー部品。
[2]
前記酸化物被膜の平均厚みが30~150nmである[1]に記載のファスナー部品。
[3]
前記酸化物被膜は、前記母材の表面の全部を被覆する[1]又は[2]に記載のファスナー部品。
[4]
前記酸化物被膜の表面の色調は、Lab表色系で表して、L*が50~80、a*が-10~10、b*が-15~15の範囲内にある[1]~[3]の何れかに記載のファスナー部品。
[5]
母材が、Alを0~4.3質量%、Cuを0~1.25質量%、Mgを0~0.06質量%、Feを0~0.10質量%含有し、残部がZn及び不可避的不純物からなる組成を有する[1]~[4]の何れかに記載のファスナー部品。
[6]
母材が、Alを3.5~4.3質量%、Cuを0.75~1.25質量%、Mgを0.02~0.06質量%、Feを0~0.10質量%含有し、残部がZn及び不可避的不純物からなる組成を有する[1]~[4]の何れかに記載のファスナー部品。
[7]
前記母材の表面と前記酸化物被膜の表面の間のLab表色系における色差ΔE* abが20以下である[1]~[6]の何れかに記載のファスナー部品。
[8]
前記酸化物被膜の表面の少なくとも一部を被覆する透明樹脂層を更に備えており、当該透明樹脂層の表面の色調は、Lab表色系で表して、L*が55~85、a*が-4~2、b*が-3~6の範囲内にある[1]~[7]の何れかに記載のファスナー部品。
[9]
前記透明樹脂層の平均厚みが0.5~30μmである[8]に記載のファスナー部品。
[10]
前記母材の表面と前記透明樹脂層の表面の間のLab表色系における色差ΔE* abが10以下である[8]又は[9]に記載のファスナー部品。
[11]
前記ファスナー部品がスライドファスナーのスライダー胴体であり、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した後に、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である[1]~[10]の何れかに記載のファスナー部品。
[12]
前記ファスナー部品がスライドファスナーのエレメントであり、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した後に、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である[1]~[10]の何れかに記載のファスナー部品。
[13]
前記ファスナー部品がスライドファスナーの下止具であり、ファスナーテープに加締め固定後、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である[1]~[10]の何れかに記載のファスナー部品。
[14]
前記ファスナー部品がボタンのキャップであり、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である[1]~[10]の何れかに記載のファスナー部品。
[15]
ダイカスト品である[1]~[14]の何れかに記載のファスナー部品。
[16]
[1]~[15]の何れかに記載のファスナー部品を備えたファスナー製品。
本発明が対象とするファスナー部品としては、ファスナー製品の部品であれば特に制限はないが、代表的にはスライドファスナーの部品及びボタンの部品が挙げられる。スライドファスナーの部品としては、スライダー、エレメント、上止具、下止具、及び引手が挙げられる。ボタンの部品としては、キャップ及びボディが挙げられる。これらの部品は、プレス加工品として提供されてもよいが、純亜鉛又は亜鉛合金が多用されるダイカスト品として提供されるのが好ましい。ファスナー製品の部品の中でもとりわけダイカストスライダーに好適に適用可能である。
一例としてファスナー部品がスライドファスナーのスライダー胴体である場合、スライダー胴体に対して、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した後に、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバを2以上とすることができる。
別の例としてファスナー部品がスライドファスナーのエレメントである場合、エレメントに対して、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した後に、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバを2以上とすることができる。
更に別の例としてファスナー部品がスライドファスナーの下止具である場合、ファスナーテープに加締め固定後、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバを2以上とすることができる。
更に別の例としてファスナー部品がボタンのキャップである場合、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバを2以上とすることができる。
本発明に係るファスナー部品の一実施形態においては、純亜鉛又は亜鉛合金を母材とする。一実施形態において、母材は、Alを0~4.3質量%、Cuを0~1.25質量%、Mgを0~0.06質量%、Feを0~0.10質量%含有し、残部がZn及び不可避的不純物からなる組成を有する。当該組成は純亜鉛及び亜鉛合金の両者を包含する。
本発明に係るファスナー部品の一実施形態においては、上記母材の表面の少なくとも一部を被覆するジルコニウムの酸化物被膜を備える。典型的には、ジルコニウムの酸化物被膜はZrO2を含有する。耐食性を向上させるという観点及び均一な色調を付与するという観点から、ジルコニウムの酸化物被膜は上記母材の表面の面積の60%以上を被覆することができ、80%以上を被覆することもでき、95%以上を被覆することもでき、全部を被覆することもできる。
本発明に係るファスナー部品の一実施形態においては、上記酸化物被膜の表面の少なくとも一部を被覆する透明樹脂層を更に備えることができる。透明樹脂層は色調の更なる調整を目的として形成することができる。均一な色調を付与するという観点から、透明樹脂層は上記酸化物被膜の表面の面積の60%以上を被覆することができ、80%以上を被覆することもでき、95%以上を被覆することもでき、全部を被覆することもできる。
ファスナー部品の母材の表面にジルコニウムの酸化物被膜を形成する方法としては、例えば、化成処理が挙げられる。化成処理は例えば脱脂工程→水洗工程→化成処理工程→水洗工程→乾燥工程の順に行うことができる。化成処理は必要に応じて繰り返し実施してもよい。
ジルコニウムの酸化物被膜の表面の少なくとも一部を被覆する透明樹脂層を形成する方法としては、クリア塗料をジルコニウムの酸化物被膜の表面に塗装する方法が挙げられる。クリア塗料の塗装は例えば塗装工程→予備乾燥(セッティング)工程→乾燥工程の順に行うことができる。クリア塗料の塗装は必要に応じて繰り返し実施してもよい。
(実施例1)
JIS H5301:1990に規定される亜鉛合金ダイカスト1種(ZDC1)を原料とし、ダイカスト成形により、スライダー胴体(YKK株式会社製型式5MDA81)を製造した。
化成処理におけるスライダー胴体の浸漬時間を表1に記載の時間に変更した他は、実施例1と同じ方法で母材の表面全体がジルコニウムの酸化物被膜で被覆されたスライダー胴体を作製した。スライダー胴体は下記の試験に必要な数を作製した。
実施例1と同じ方法で、母材の表面全体がジルコニウムの酸化物被膜で被覆されたスライダー胴体を作製した。次いで、市販のエポキシ樹脂を含有するクリア塗料(関西ペイント株式会社製商品名EU塗料クリヤー)を、クリア塗料:シンナー=1:3の体積比で混合することで希釈した。希釈されたクリア塗料(約22℃)を回転バレルスプレー方式で2分間、当該スライダー胴体の全面に塗装した。次いで、クリア塗料を塗装後のスライダー胴体に対して、90℃の熱風を2.5分間吹き付ける予備乾燥を行い、更に130℃の熱風を15分間吹き付ける乾燥を行った。その後、室温で空冷した。これにより、ジルコニウムの酸化物被膜の表面全体が透明樹脂層で被覆されたスライダー胴体を作製した。スライダー胴体は下記の試験に必要な数を作製した。
実施例2と同じ方法で、母材の表面全体がジルコニウムの酸化物被膜で被覆されたスライダー胴体を作製した。次いで、当該スライダー胴体に対して実施例4と同じ方法でクリア塗料を塗装し、ジルコニウムの酸化物被膜の表面全体が透明樹脂層で被覆されたスライダー胴体を作製した。スライダー胴体は下記の試験に必要な数を作製した。
実施例3と同じ方法で、母材の表面全体がジルコニウムの酸化物被膜で被覆されたスライダー胴体を作製した。次いで、当該スライダー胴体に対して実施例4と同じ方法でクリア塗料を塗装し、ジルコニウムの酸化物被膜の表面全体が透明樹脂層で被覆されたスライダー胴体を作製した。スライダー胴体下記の試験に必要な数を作製した。
実施例1で作製したスライダー胴体に対して、アルカリ脱脂及び水洗後、市販のリン酸亜鉛用表面調整剤(日本ペイント・サーフケミカルズ株式会社製サーフファインGL1)にて表面調整を行った。表面調整は、25℃に調整した表面調整液にスライダー胴体を30秒間浸漬させることにより行った。次いで、市販のリン酸亜鉛を含有する化成処理液(日本ペイント・サーフケミカルズ株式会社製サーフダインEC1000)を使用し、化成処理を行った。化成処理は、50℃に調整したリン酸亜鉛系化成処理液にスライダー胴体を100秒間浸漬させることにより行った。化成処理後は、水洗を行い、60℃の温風を20分間吹き付ける乾燥を行った。その後、室温で空冷した。これにより、母材の表面全体がリン酸亜鉛被膜で被覆されたスライダー胴体を作製した。スライダー胴体は下記の試験に必要な数を作製した。
実施例1で作製したスライダー胴体に対して、アルカリ脱脂及び水洗後、硝酸クロム、硝酸コバルト、無機酸、及びケイ素化合物を含有する三価クロム系化成処理液を使用し、化成処理を行った。化成処理は、25℃に調整した三価クロム系化成処理液にスライダー胴体を60秒間浸漬させることにより行った。化成処理後は、水洗を行い、60℃の温風を20分間吹き付ける乾燥を行った。その後、室温で空冷した。これにより、母材の表面全体が三価クロム被膜で被覆されたスライダー胴体を作製した。スライダー胴体は下記の試験に必要な数を作製した。
実施例1~6及び比較例1~2のスライダー胴体の裏側中央部の平坦面に対して、先述した方法により測色を行った。測色は池上通信機株式会社製の色彩色差計(商品名:RTC-21(ILOREAL Real True Color XYZカメラ))を用いて行い、XYZ表色系(CIE(国際照明委員会)が1931年に採択した標準表色系)の色情報を得て、当該色彩色差計の機能によってLab表色系におけるL*、a*、b*に変換した。測色条件は、一箇所当たりの測色面積0.5mm2、温度15~30℃、湿度30~75%RHの条件とした。光源はドーム型LED照明(色温度8500K)を使用した。実施例1~3は、ジルコニウムの酸化物被膜の表面の色調が測定され、実施例4~6は、透明樹脂層の表面の色調が測定された。比較例1はリン酸亜鉛被膜の表面の色調が測定され、比較例2は三価クロムの表面の色調が測定された。また、実施例1~6及び比較例1~2のスライダー胴体に対して化成処理前に母材の表面に対して同様の方法で測色した。結果を表1に示す。なお、a*及びb*は色調を表し、a*はマゼンタ-緑系の色調(+はマゼンタ寄り、-は緑寄り)を表し、b*は黄-青系の色調(+は黄寄り、-は青寄り)を表す。L*は明度を表し、値が大きいと光沢感が高い。
実施例1~6のスライダー胴体の裏側中央部の平坦面を酸化物被膜(及び透明樹脂層)の厚み方向に切断して断面を露出し、先述した方法により、ジルコニウムの酸化物被膜の平均厚み、及び、透明樹脂層の平均厚みを測定した。ジルコニウムの酸化物被膜(及び透明樹脂層)の断面を露出させるためのスライダー胴体の切断は、樹脂包埋した後に機械研磨を施し、クロスセクションポリッシャ(CP加工)することにより行った。ジルコニウムの酸化物被膜(及び透明樹脂層)の断面観察は、走査型電子顕微鏡(SEM)(株式会社日立ハイテク製型式S-4800)を使用して加圧電圧2kV、プローブ電流80μA、作動距離(WD)約4mmで行った。
結果を表1に示す。
実施例1~6のスライダー胴体を、YKK株式会社製商品名5RGPSのスライドファスナーチェーンに挿通して、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した。次いで、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施し、スライダー胴体に対するレイティングナンバを決定した。結果を表1に示す。なお、比較例1~2については、望ましい色調が得られなかったため、耐水性評価を実施しなかった。
表1の結果より、ジルコニウムの酸化物被膜によって被覆された亜鉛合金製のスライダー胴体は、リン酸亜鉛処理又はクロメート処理を受けた場合に比べて母材の色調に近かったことが理解できる。また、ジルコニウムの酸化物被膜の表面を更に透明樹脂層で被覆すると、母材の色調に更に近づけることができたことが理解できる。ジルコニウムの酸化物被膜及び透明樹脂層は耐食性に優れていることが確かめられた。
2 :芯部
3 :エレメント
4 :上止具
5 :下止具
6 :スライダー
7 :スライドファスナーチェーン
8 :異形線
9 :係合頭部
10 :脚部
11 :矩形線
12 :異形線
30 :キャップ
31 :天板
32 :周側板
61 :スライダー胴体
62 :引手
110 :母材
120 :酸化物被膜
Claims (16)
- 純亜鉛又は亜鉛合金製の母材と、当該母材の表面の少なくとも一部を被覆するジルコニウムの酸化物被膜とを備えたファスナー部品。
- 前記酸化物被膜の平均厚みが30~150nmである請求項1に記載のファスナー部品。
- 前記酸化物被膜は、前記母材の表面の全部を被覆する請求項1又は2に記載のファスナー部品。
- 前記酸化物被膜の表面の色調は、Lab表色系で表して、L*が50~80、a*が-10~10、b*が-15~15の範囲内にある請求項1~3の何れか一項に記載のファスナー部品。
- 母材が、Alを0~4.3質量%、Cuを0~1.25質量%、Mgを0~0.06質量%、Feを0~0.10質量%含有し、残部がZn及び不可避的不純物からなる組成を有する請求項1~4の何れか一項に記載のファスナー部品。
- 母材が、Alを3.5~4.3質量%、Cuを0.75~1.25質量%、Mgを0.02~0.06質量%、Feを0~0.10質量%含有し、残部がZn及び不可避的不純物からなる組成を有する請求項1~4の何れか一項に記載のファスナー部品。
- 前記母材の表面と前記酸化物被膜の表面の間のLab表色系における色差ΔE* abが20以下である請求項1~6の何れか一項に記載のファスナー部品。
- 前記酸化物被膜の表面の少なくとも一部を被覆する透明樹脂層を更に備えており、当該透明樹脂層の表面の色調は、Lab表色系で表して、L*が55~85、a*が-4~2、b*が-3~6の範囲内にある請求項1~7の何れか一項に記載のファスナー部品。
- 前記透明樹脂層の平均厚みが0.5~30μmである請求項8に記載のファスナー部品。
- 前記母材の表面と前記透明樹脂層の表面の間のLab表色系における色差ΔE* abが10以下である請求項8又は9に記載のファスナー部品。
- 前記ファスナー部品がスライドファスナーのスライダー胴体であり、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した後に、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である請求項1~10の何れか一項に記載のファスナー部品。
- 前記ファスナー部品がスライドファスナーのエレメントであり、JIS S3015:2019に従って測定される往復開閉耐久試験を実施した後に、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である請求項1~10の何れか一項に記載のファスナー部品。
- 前記ファスナー部品がスライドファスナーの下止具であり、ファスナーテープに加締め固定後、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である請求項1~10の何れか一項に記載のファスナー部品。
- 前記ファスナー部品がボタンのキャップであり、JIS Z2371:2015に従って測定される中性塩水噴霧試験を実施した時のレイティングナンバが2以上である請求項1~10の何れか一項に記載のファスナー部品。
- ダイカスト品である請求項1~14の何れか一項に記載のファスナー部品。
- 請求項1~15の何れか一項に記載のファスナー部品を備えたファスナー製品。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2023/021417 WO2024252634A1 (ja) | 2023-06-08 | 2023-06-08 | ファスナー部品 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2023/021417 WO2024252634A1 (ja) | 2023-06-08 | 2023-06-08 | ファスナー部品 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024252634A1 true WO2024252634A1 (ja) | 2024-12-12 |
Family
ID=93795726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/021417 Ceased WO2024252634A1 (ja) | 2023-06-08 | 2023-06-08 | ファスナー部品 |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024252634A1 (ja) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001008714A (ja) * | 1999-06-30 | 2001-01-16 | Ykk Corp | 構成部材付き被着物の製造方法および構成部材付き被着物 |
| JP3197413U (ja) * | 2015-02-24 | 2015-05-14 | Ykk株式会社 | レモンゴールド色を有する金属製ファスナー部材及びそれを備えたファスナー |
| WO2022030564A1 (ja) * | 2020-08-04 | 2022-02-10 | Ykk株式会社 | スライドファスナエレメントおよびスライドファスナストリンガ |
| WO2022123709A1 (ja) * | 2020-12-10 | 2022-06-16 | Ykk株式会社 | スライドファスナー用スライダーとその製造方法 |
| WO2022210222A1 (ja) * | 2021-03-31 | 2022-10-06 | Ykk株式会社 | 着色された金属製エレメントを有するスライドファスナストリンガの製造方法、金属製エレメント、スライドファスナストリンガ、及びスライドファスナチェーン |
-
2023
- 2023-06-08 WO PCT/JP2023/021417 patent/WO2024252634A1/ja not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001008714A (ja) * | 1999-06-30 | 2001-01-16 | Ykk Corp | 構成部材付き被着物の製造方法および構成部材付き被着物 |
| JP3197413U (ja) * | 2015-02-24 | 2015-05-14 | Ykk株式会社 | レモンゴールド色を有する金属製ファスナー部材及びそれを備えたファスナー |
| WO2022030564A1 (ja) * | 2020-08-04 | 2022-02-10 | Ykk株式会社 | スライドファスナエレメントおよびスライドファスナストリンガ |
| WO2022123709A1 (ja) * | 2020-12-10 | 2022-06-16 | Ykk株式会社 | スライドファスナー用スライダーとその製造方法 |
| WO2022210222A1 (ja) * | 2021-03-31 | 2022-10-06 | Ykk株式会社 | 着色された金属製エレメントを有するスライドファスナストリンガの製造方法、金属製エレメント、スライドファスナストリンガ、及びスライドファスナチェーン |
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