ZIPPER SLIDE AND ZIPPER

Abstract

A zipper slider comprising: a slider body; a pull tab; and a locking pin. The locking pin is made of stainless steel. A black oxide layer is formed on one surface of the locking pin. The surface of the locking pin has a brightness L* sufficient to 31.70 ≤ L* ≤ 35.90, and an a* value sufficient to -0.708 ≤ a* ≤ 1.929, where the brightness L* and the a* value correspond to definitions in a CIELAB color space as defined in JIS Z8781-4 (2013).

Description

TECHNICAL AREA

[0001] The present invention relates to a zipper slider, in particular a slider with a black locking pin, and to a zipper. GENERAL STATE OF THE ART

[0002] One type of zipper slider has a function of preventing the slider from moving up and down unintentionally by engaging a locking claw with a link, depending on the actuation state of a pull piece. Such a slider is sometimes referred to as an automatic-stop zipper slider or a self-locking slider. Among automatic-stop zipper sliders, there is one type that includes a component (hereafter referred to simply as the "locking pin") incorporating a locking claw for engaging a link to prevent the slider from moving, and a leaf spring for actuating the locking claw between a locked position and an unlocked position. For example, there is a slider such as that disclosed in Patent Document 1 and Patent Document 2.

[0003] The slide of patent document 1 is a slide with a shape and structure suitable for manufacturing a slide body by zinc die-casting, and the slide of patent document 2 is a slide with a shape and structure suitable for manufacturing a slide body by pressing a copper-zinc alloy. A slide provided with a locking pin engaging the locking claw and leaf spring, as described in patent document 1 and patent document 2, is sometimes referred to as a "semi-automatic slide" or "semi-automatic locking slide" and is referred to in this description as a "semi-automatic slide" or simply as a "slide". LIST OF PUBLICATIONS PATENT DOCUMENTS Patent document 1: WO2016 / 092637A1 Patent Document 2: JP2002-010808A

[0004] Since the locking pin in such a semi-automatic slide must have sufficient strength to maintain the locked state and high resistance to repeated elastic deformation, stainless steel is often used.

[0005] Such a semi-automatic slider can easily prevent the zipper from being accidentally opened and is therefore frequently used in the prior art as a zipper slider on the front placket of garments such as jeans or jackets. When used for such clothing applications, the slider of the type disclosed in Patent Document 1 has its slider body manufactured by zinc die-casting, and the original color of the zinc material is used unchanged to obtain an approximately silver hue, which was common practice in the past. Furthermore, as in Patent Document 2, when using a copper-zinc alloy such as red brass or brass as the material for the slider body and the pull tab for clothing applications such as...Jeans often use the copper-zinc alloy either in its original color to obtain an almost golden hue, or in a silver color, which is obtained in the prior art by copper-tin plating on the surface.

[0006] In such clothing applications, the stainless steel locking pin has a silver hue as its original color. Therefore, if the slide body has a golden hue, the stainless steel locking pin is subjected to atmospheric heat treatment to oxidize it, thus adjusting its hue to the golden tone before use. If the slide body is silver, as described above, the locking pin, whose hue has been changed to a golden tone by atmospheric heat treatment, is acid-washed to restore its original silver color. Semi-automatic slides have frequently been used in the manner described above in the prior art.In recent years, however, there has been a need to use the semi-automatic slider on a bag or the like, and in such a case it is required that the color of the slider, apart from gold and silver in the prior art, be black, which is a color commonly used on bags or the like.

[0007] When a semi-automatic slide valve is blackened, it is generally referred to as black. However, in reality, there isn't just one set of black shades, but rather different types of black due to variations in the absorption and reflection of visible light. While the locking pin is made of stainless steel, the slide valve body is not, and the two components are assembled as separate parts after machining. Therefore, the black shades of the two components are not exactly the same, and the two parts may appear different. Particularly in recent years, even with the same black shade, a product with a lower reflection and higher absorption of visible light—that is, a product that is uniformly pure black—is sometimes preferred.In such a case, the black color of these parts, even if only a few parts are not pure black, however small these parts may be, appears different from the pure black of the entire product, which can give a negative impression in terms of appearance. Furthermore, if the zipper is used on wetsuits or hunting apparel and a small part of the product is a different color than the rest of the product, which is pure black, this part may stand out, or stand out at certain angles, because it reflects visible light. This can attract sharks or other wild and dangerous animals, limit the zipper's uses, and also make it look unattractive.

[0008] Such a subtle difference in hue occurs not only with black, but also with prior art colors such as gold and silver. However, in the case of a color composed of reflected light with strong directional properties, such as gold and silver, it is natural that the appearance and luster change depending on the angle at which the light is reflected. Therefore, it is rather unlikely that any feeling of discomfort will be experienced, even if there is a slight difference in appearance between the color of the slide body and the color of the locking pin. In the case of colors that exhibit color through the absorption of visible light, such as black, however, a color difference may be easily noticeable depending on the degree of blackening. BRIEF DESCRIPTION OF THE INVENTIONAL PROBLEM

[0009] There are several ways to blacken a stainless steel locking pin, including plating or painting. Plating requires applying multiple coats of primer to a stainless steel base to create a black plating layer with sufficient adhesion. This method is complex and costly. Painting, on the other hand, is susceptible to peeling because the locking pin is a component subject to significant friction and elastic deformation.

[0010] The present invention was developed by focusing on the discomfort that people experience due to subtle color differences in such black components. The object of the present invention is to provide a locking pin for a zipper that is designed to have a black color that blends in with surrounding components without causing discomfort, using a method that requires lower manufacturing costs and exhibits sufficient adhesive strength. SOLUTION TO THE PROBLEM

[0011] To solve the above problem, a zipper slider according to the present invention has the following features.

[0012] A zipper slider (20, 30) comprises: a slider body (23, 33); a pull piece (25, 35); and a locking pin (21, 31), wherein the locking pin (21, 31) is made of stainless steel, has a black oxide layer on a surface of the locking pin (21, 31), and the surface of the locking pin (21, 31) has a brightness L* that satisfies 31.70 ≤ L* ≤ 35.90 and an a* value that satisfies -0.708 ≤ a* ≤ 1.929, wherein the brightness L* and the a* value correspond to definitions in a CIELAB color space defined in JIS Z8781-4 (2013).

[0013] Furthermore, the surface of the locking pin (21, 31) has a b* value that satisfies -2.428 ≤ b* ≤ 0.466, where the b* value corresponds to a definition in the CIELAB color space defined in JIS Z8781-4 (2013).

[0014] Preferably, the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 10 wt% to 14 wt% nickel, and the surface of the locking pin (21, 31) has a brightness L* that satisfies 31.70 ≤ L* ≤ 34.16, an a* value that satisfies 0.369 ≤ a* ≤ 1.736, and a b* value that satisfies -2.428 ≤ b* ≤ 0.466, wherein the brightness L*, the a* value, and the b* value correspond to definitions in the CIELAB color space defined in JIS Z8781-4 (2013).Alternatively, the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 13 wt% to 17 wt% manganese, and the surface of the locking pin (21, 31) has a brightness L* that satisfies 33.04 ≤ L* ≤ 35.90, an a* value that satisfies -0.708 ≤ a* ≤ 1.929, and a b* value that satisfies -2.388 ≤ b* ≤ -1.495, where the brightness L*, the a* value, and the b* value correspond to definitions in the CIELAB color space defined in JIS Z8781-4 (2013).

[0015] Preferably, the sliding body (23, 33) is black, and according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013), a difference ΔL* between the brightness L* of the sliding body (23, 33) and the brightness L* of the locking pin (21, 31) satisfies the condition ΔL* ≤ 8.54, and a difference Δa* between the a* value of the sliding body (23, 33) and the a* value of the locking pin (21, 31) satisfies the condition 0.03 ≤ Δa* ≤ 2.67.

[0016] If the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 10 wt% to 14 wt% nickel, the slide body (23, 33) is preferably black, and according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013), a difference ΔL* between the brightness L* of the slide body (23, 33) and the brightness L* of the locking pin (21, 31) satisfies the condition ΔL* ≤ 6.79, and a difference Δa* between the a* value of the slide body (23, 33) and the a* value of the locking pin (21, 31) satisfies the condition 1.11 ≤ Δa* ≤ 2.47.If the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 13 wt% to 17 wt% manganese, the slide body (23, 33) is preferably black, and according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013), a difference ΔL* between the brightness L* of the slide body (23, 33) and the brightness L* of the locking pin (21, 31) satisfies the condition ΔL* ≤ 8.54, and a difference Δa* between the a* value of the slide body (23, 33) and the a* value of the locking pin (21, 31) satisfies the condition 0.03 ≤ Δa* ≤ 2.67.

[0017] Furthermore, a zipper preferably comprises the following: the zipper slider described above, wherein a link of the zipper is made of ferritic stainless steel and the link has a brightness L* that satisfies 29.67 ≤ L* ≤ 36.24, an a* value that satisfies -0.63 ≤ a* ≤ 0.76, and a b* value that satisfies 0.42 ≤ b* ≤ 1.22, wherein the brightness L*, the a* value, and the b* value correspond to definitions in the CIELAB color space defined in JIS Z8781-4 (2013). In this case, the slider body (23, 33) is preferably black, and according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013), a difference ΔL* between the brightness L* of the element and the brightness L* of the slider body (23, 33) satisfies the condition ΔL* ≤ 8.94, and a difference Δa* between their a* values ​​satisfies the condition 0.11 ≤ Δa* ≤ 1.49.

[0018] Furthermore, in the zipper slider according to the embodiment of the present invention, the oxide layer on the surface of the locking pin (21, 31) has a thickness of 320 nm or more and 1870 nm or less. In some embodiments, the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 10% or more by weight and 14% or less by weight of nickel, and the thickness of the oxide layer on the surface of the locking pin (21, 31) is 320 nm or more and 1260 nm or less. In some other embodiments, the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 13 wt. percent or more and 17 wt. percent or less manganese, and the thickness of the oxide layer on the surface of the locking pin (21, 31) is 440 nm or more and 1870 nm or less.In a zipper that uses the slider according to the embodiment of the present invention, the thickness of an oxide layer on the link of the zipper is preferably 1010 nm or more and 2700 nm or less. ADVANTAGEOUS EFFECTS OF THE INVENTION

[0019] In accordance with the design of the zipper slider of the present invention, the black color of the zipper slider does not cause any discomfort with the overall product, even if a user desires that a product utilizing the zipper be black, a color that exhibits a low reflectance and high absorption of visible light. Furthermore, the manufacturing costs are lower compared to blackening by plating. Additionally, the problem of adhesion of a colored layer, which occurs during painting, is also improved. BRIEF DESCRIPTION OF THE DRAWINGS Fig.Figure 1 is a perspective view of a zipper slider according to a first embodiment of the present invention. Fig. Figure 2 is a sketch illustrating three components forming the zipper slider according to the first embodiment of the present invention, in a disassembled state. Fig. Figure 3 is a perspective view of a zipper slider according to a second embodiment of the present invention. Fig. Figure 4 is a sketch illustrating three components forming the zipper slider according to the second embodiment of the present invention, in a disassembled state. Fig. Figure 5 is a schematic sketch showing an oxide layer formed on a surface of a locking pin of the zipper slider according to the present invention. Fig.Figure 6 is a graph showing results of a distribution state of metal elements contained in a black oxide layer formed on a surface of a locking pin of Example 1-16, analyzed in a depth direction by Auger electron spectroscopy. Fig. 7 is a graph for example 1-17, as above. Fig. Figure 8 is a graph for example 1-18, as above. Fig. Figure 9 is a graph for example 1-19, as above. Fig. 10 is a graph for example 1-20, as above. Fig. 11 is a graph for example 1-21, as above. Fig. 12 is a graph for example 2-16, as above. Fig. 13 is a graph for example 2-17, as above. Fig. 14 is a graph for example 2-18, as above. Fig.15 is a graph for example 2-19, as above. Fig. 16 is a graph for example 2-20, as above. Fig. 17 is a graph for example 2-21, as above. Fig. Figure 18 is a graph for comparison example 1-2, as in the preceding one. Fig. Figure 19 is a graph for comparison example 1-3, as in the preceding one. Fig. 20 is a graph for comparison example 2-2, as in the preceding one. Fig. 21 is a graph for comparison example 2-3, as in the preceding one. Fig. 22 is a graph for comparison example 3, as in the preceding one. Fig.Figure 23 is a graph showing results of a distribution state of metal elements contained in a black oxide layer formed on a surface of a zipper dome link of Example 3-16, analyzed in a depth direction by Auger electron spectroscopy. Fig. 24 is a graph for example 3-17, as above. Fig. 25 is a graph for example 3-18, as above. Fig. 26 is a graph for example 3-19, as above. Fig. 27 is a graph for example 3-20, as above. Fig. 28 is a graph for example 3-21, as above. DESCRIPTION OF THE EXECUTION FORMS

[0020] The following is a description of embodiments of the present invention with reference to the drawings.

[0021] Fig.Figure 1 is a perspective view of a zipper slider 20 according to a first embodiment of the present invention. As in Fig. As shown in Figure 2, the slide 20 comprises at least three components, namely a locking pin 21, a slide body 23, and a pull piece 25. The slide body 23 of the slide 20 is shown in Figure 2. Fig.The type shown in Figure 1 is a slide with a shape and structure suitable for manufacture by die casting using a zinc material. The locking pin 21 must have sufficient strength to maintain a stopped, locked state of the slide 20 and must also exhibit high resistance to repeated elastic deformation; therefore, it is made of stainless steel. The pull piece 25 is made of a suitable material such as zinc or a copper-zinc alloy. The locking pin 21, the slide body 23, and the pull piece 25 are each manufactured as separate components in separate processes. Subsequently, the pull piece 25 is clamped to the slide body 23, and the locking pin 21 is attached to the body 23, thus forming the slide 20 as the finished product.

[0022] In the present embodiment, during the manufacture of each of the components—locking pin 21, slide body 23, and pull piece 25—the locking pin 21, the slide body 23, and the pull piece 25 are all colored to have a black appearance. The body 23 is preferably colored black by painting. A metal section of the pull piece 25 can also be colored by painting, and if necessary, a black rubber material can be formed in one piece around the metal section to form an overall black rubber pull piece. The slide body 23 and the pull piece 25 can be colored black by plating or chemical conversion treatment instead of painting. The locking pin 21 can be colored black by painting or plating, but in the present embodiment, the locking pin 21 is colored black by chemical conversion treatment.The blackening treatment of the locking pin 21 will be described in more detail later.

[0023] Fig. Figure 3 is a perspective view of a zipper slider 30 according to a second embodiment of the present invention. As in Fig. As shown in Figure 4, the slide 30 comprises at least three components: a locking pin 31, a slide body 33, and a pull piece 35. The slide body 33 of the slide 30 is shown in Figure 4. Fig.The type shown in Figure 3 has a shape and structure suitable for manufacture by pressing a copper-zinc alloy. The locking pin 31 must have sufficient strength to maintain a stopped, locked state of the slide 30 and must also exhibit high resistance to repeated elastic deformation; therefore, it is made of stainless steel. The pull piece 35 is made of a suitable material, such as a copper-zinc alloy. The locking pin 31, the slide body 33, and the pull piece 35 are each manufactured as separate components in separate processes. Subsequently, the pull piece 35 and the locking pin 31 are attached to the slide body 33 to form the slide 30 as the finished product.

[0024] In the second embodiment of the present invention, during the manufacture of each of the components locking pin 31, slide body 33, and pull piece 35, the locking pin 31, the slide body 33, and the pull piece 35 are all colored to have a black appearance. The body 33 and the pull piece 35 are preferably colored black by plating, but can also be colored black by painting or chemical conversion treatment. The locking pin 31 can also be colored by plating or painting, but in the present embodiment, the locking pin 31 is colored black by chemical conversion treatment.

[0025] Note that the slide 20, 30 has a structure comprising at least three components, as shown in Fig.1 to 4 shown, which can be referred to as a “semi-automatic slide” or “semi-automatic locking slide”, as described above, but in the present description the slide 20, 30 is simply referred to as “slide 20, 30”.

[0026] Next, the blackening treatment of the locking pin 21, 31 in the embodiments of the present invention is described. If the locking pin 21, 31, made of stainless steel, is to be blackened with respect to the black slide body 23, 33, methods such as painting, plating, and chemical conversion treatment are conceivable as methods for blackening the locking pin 21, 31. However, if painting is used for the blackening treatment of the locking pin 21, 31 made of stainless steel, the paint on the locking pins tends to flake off, since the locking pin is a part that is subject to repeated elastic deformation or is a component that is subject to strong friction due to metal-to-metal contact with a pull piece, washing, or the like, and a quality defect is likely to occur with long-term use.And if plating is used for the blackening treatment of the locking pin 21, 31 made of stainless steel, it is difficult to laminate a black plating layer with good adhesion directly onto a stainless steel base material. Therefore, to improve adhesion, several layers of primer plating must be applied, which has the disadvantage of increasing manufacturing costs. Furthermore, both painting and plating require increasing the thickness of the paint or plating layer to obtain a black color with low reflectance and high absorption of visible light. This has the disadvantage of obscuring the texture of the stainless steel of the locking pin due to the coating. For this reason, in the present invention, an oxide layer is formed by chemical conversion treatment during the blackening treatment of the locking pin 21, 31. Fig. Figure 5 is a schematic diagram showing an oxide layer formed on a surface of the locking pin 21, 31 of the zipper slider according to the present invention. An oxide layer 53 is formed on a surface of a base material 51 of the locking pin 21, 31.

[0027] Prior art attempts have been made to blacken the locking pin 21, 31 by chemical conversion treatment, and it was possible to blacken the locking pin 21, 31 by a relatively simple process. A widely used chemical conversion treatment is a process that includes pretreatment processes such as polishing, heat treatment, and removal of any naturally formed oxide layer on a stainless steel component, followed by immersion in an acidic solution (a chromic acid-based solution) or an alkaline solution (a caustic soda-based solution) to form an oxide layer, and subsequent cleaning and drying as a post-treatment.

[0028] Even though the oxide layer is formed through chemical transformation treatment, depending on the state of the oxide layer and the angle at which the locking pin 21, 31 is viewed, the color may not be completely black (black as an object that completely absorbs visible light) due to the degree of light reflection, but rather appear brownish due to the reflection of some of the visible light. In such a case, depending on the viewing angle, the black color of the product on which the zipper is used (bags, clothing, or the like), the black color of the slider body 23, 33, and the black color of the locking pin 21, 31 do not appear as the same black color, causing a feeling of visual discomfort.The reason for this is that it was not possible to make the oxide layer thick enough to reduce the reflection of visible light to such an extent that it becomes almost completely black, and to absorb the visible light to such an extent that it becomes almost completely black. Therefore, in the present invention, an oxide layer thickness is formed that is sufficient to reduce the reflection of visible light to such an extent that it is almost completely black, which is not possible with the locking pin 21, 31 according to the prior art chemical conversion treatment.

[0029] Next, the results of the measurement of the brightness and hue of the locking pin 21, 31 according to the embodiment of the present invention are described.

[0030] As factors for evaluating the degree of blackening of the slide 20, 30 and the locking pin 21, 31 in the embodiments of the present invention, a value a*, a value b*, and a value L* in the CIELAB color space defined in JIS Z8781-4 (2013) were used. Here, a* and b* are hues defined in the CIELAB color space defined in JIS Z8781-4 (2013). a* represents a magenta-green hue (+ is closer to magenta, - is closer to green), and b* represents a yellow-blue hue (+ is closer to yellow, - is closer to blue). L* indicates the brightness defined in the CIELAB color space defined in JIS Z8781-4 (2013), with a higher value indicating higher gloss. The color measurement was performed using a device provided by Ikegami Tsushinki Co. Ltd. The test was carried out on the manufactured RTC-21. The light source is an LED light.

[0031] Examples 1-1 to 1-15 shown in Table 1 are locking pins 21, 31 according to the embodiment of the present invention, made of a nickel-based austenitic stainless steel with a nickel content of 10 to 14%, and in particular locking pins 21, 31 according to the embodiment of the present invention, made of a nickel-based austenitic stainless steel containing 12 wt% nickel, 20 wt% chromium, and 3 wt% manganese. The external appearance of each of Examples 1-1 to 1-15 is a deep and rich black color, and there is almost no change in appearance depending on the angle of reflection of light.Table 1 shows the results of the measurement of the value of brightness L*, the value of a* and the value of b* from Example 1-1 to Example 1-15 as well as the results of their comparison with the value of brightness L*, the value of a* and the value of b* of the slide body 23, 33.

[0032] “Difference in brightness ΔL* from the body” denotes a value obtained by subtracting the “brightness L* of the slider body” from the “measured brightness L* of each example”, “color difference Δa* from the body” denotes a value obtained by subtracting the “measured a* of the slider body” from the “measured a* of each example”, and “color difference Δb* from the body” denotes a value obtained by subtracting the “measured b* of the slider body” from the “measured b* of each example” (the same applies to Tables 2, 3 and 4 below).

[0033] Examples 2-1 to 2-15 shown in Table 2 are locking pins 21, 31 according to the embodiment of the present invention, made of a manganese-based austenitic stainless steel with a manganese content of 13 to 17%, and in particular locking pins 21, 31 according to the embodiment of the present invention, made of a manganese-based austenitic stainless steel containing 15 wt% manganese, 4 wt% nickel, and 17 wt% chromium. The external appearance of each of Examples 2-1 to 2-15 is a deep and rich black color, and there is almost no change in appearance depending on the angle of reflection of light.Table 2 shows the results of the measurement of the value of brightness L*, the value of a* and the value of b* from Example 2-1 to Example 2-15 as well as the results of their comparison with the value of brightness L*, the value of a* and the value of b* of the slide body 23, 33.

[0034] Examples 3-1 to 3-15 shown in Table 3 are embodiments in which a test piece (a test piece in the shape of a zipper dome link) made of ferritic stainless steel (SUS430) was subjected to a blackening treatment by chemical transformation in the same manner as in the examples above. The external appearance of each of Examples 3-1 to 3-15 is a deep and rich black color, and there is almost no change in appearance depending on the angle of reflection of light. Table 3 shows the results of the measurement of the brightness L*, a*, and b* values ​​of Examples 3-1 to 3-15, as well as the results of comparing them with the brightness L*, a*, and b* values ​​of the slider body 23, 33. [Table 1] L* a* b* Difference ΔL* in the brightness of the body Color difference Δa* from the body Color difference Δb* from the body Example 1-1 33,56 1,19 -0,002 6,2 1,93 0,42 Example 1-2 33,63 1,186 -0,651 6,26 1,92 -0,23 Examples 1-3 34,16 1,186 0,466 6,79 1,92 0,89 Examples 1-4 34,16 1,468 -0,033 6,79 2,21 0,39 Examples 1-5 33,72 0,992 -0,773 6,35 1,73 -0,35 Examples 1-6 33,28 0,668 -2,187 5,92 1,41 -1,76 Examples 1-7 33,27 0,369 -1,745 5,91 1,11 -1,32 Examples 1-8 32,98 0,989 -1,811 5,62 1,73 -1,39 Examples 1-9 33,20 0,763 -1,809 5,83 1,50 -1,39 Example 1-10 33,37 0,458 -2,428 6,01 1,20 -2,00 Examples 1-11 32,00 1,502 -1,691 4,64 2,24 -1,27 Examples 1-12 32,28 1,652 -1,315 4,92 2,39 -0,89 Example 1-13 31,87 1,736 -1,988 4,51 2,47 -1,56 Example 1-14 32,16 1,730 -1,289 4,80 2,47 -0,87 Example 1-15 31,70 1,208 -1,361 4,34 1,95 -0,94 [Table 2] L* a* b* Difference ΔL* in the brightness of the body Color difference Δa* from the body Color difference Δb* from the body Example 2-1 35,63 1,230 -1,562 8,27 1,97 -1,14 Example 2-2 35,90 1,111 -1,842 8,54 1,85 -1,42 Example 2-3 35,48 1,929 -1,641 8,12 2,67 -1,22 Example 2-4 35,54 1,505 -2,232 8,18 2,24 -1,81 Example 2-5 35,66 1,510 -2,080 8,30 2,25 -1,66 Example 2-6 35,76 0,126 -2,381 8,40 0,86 -1,96 Example 2-7 35,32 -0,113 -2,388 7,96 0,62 -1,96 Example 2-8 35,05 0,492 -2,340 7,69 1,23 -1,92 Example 2-9 35,32 -0,708 -1,495 7,96 0,03 -1,07 Example 2-10 35,40 -0,397 -1,767 8,04 0,34 -1,34 Example 2-11 33,75 -0,029 -2,274 6,38 0,71 -1,85 Example 2-12 33,13 0,064 -2,092 5,77 0,80 -1,67 Example 2-13 33,04 0,031 -1,923 5,68 0,77 -1,50 Example 2-14 33,43 -0,022 -2,006 6,07 0,72 -1,58 Example 2-15 33,49 0,060 -1,774 6,13 0,80 -1,35 [Table 3] L* a* b* Difference ΔL* in the brightness of the body Color difference Δa* from the body Color difference Δb* from the body Example 3-1 36,17 0,4 0 8,8 1,20 1,34 Example 3-2 36,24 0,33 1,22 8,88 1,07 1,65 Example 3-3 35,95 0,31 1,04 8,58 1,05 1,47 Example 3-4 36,31 0,64 1,07 8,94 1,38 1,50 Example 3-5 36,13 0,76 1,20 8,77 1,49 1,62 Example 3-6 33,63 -0,50 1,08 6,27 0,24 1,50 Example 3-7 33,58 -0,02 1,18 6,22 0,72 1,60 Example 3-8 33,62 0,26 1,06 6,26 1,00 1,48 Example 3-9 33,45 0,28 1,19 6,09 1,02 1,61 Example 3-10 34,42 0,05 1,33 7,06 0,79 1,76 Example 3-11 29,75 -0,42 0,42 2,39 0,32 0,84 Example 3-12 30,90 -0,36 0,70 3,54 0,38 1,13 Example 3-13 29,67 -0,63 0,60 2,31 0 1,02 Example 3-14 29,92 -0,58 0,54 2,56 0,16 0,97 Example 3-15 30,20 -0,35 0,65 2,83 0,38 1,08

[0035] The slide body 23, 33 is a slide that has been blackened by painting and is coated with a paint used for black paint that has a low reflectance and a high absorption of visible light. The brightness value L* of the black paint was L* = 27.36, and the values ​​of a* and b* were a* = -0.738 and b* = -0.424.

[0036] Although the locking pin 21, 31 from Example 1-1 to Example 2-15 and the slide body 23, 33 are manufactured from different materials and treated, colored, and then assembled as separate components, the difference (ΔL*) in brightness L* between the slide body 23, 33 and the locking pin 21, 31 is kept within a low range of ΔL* ≤ 8.54. The “color difference Δa* from the body” and the “color difference Δb* from the body” are also kept low within an acceptable range, and in particular, the difference (Δa*) in the value of a* is kept low, within a range of 0.03 ≤ Δa* ≤ 2.67. This makes it less likely that there is a significant difference in the appearance of the black colors of the two components. Furthermore, the absolute value of the brightness L* satisfies the condition 31.70 ≤ L* ≤ 35.90, and the value of a* and the value of b* satisfy the conditions -0.708 ≤ a* ≤ 1.929 respectively.-2.428 ≤ b* ≤ 0.466. Therefore, the black color of the locking pin 21, 31 is a black color that has a lower reflectance and a higher absorption for visible light than the same black color referred to as pure black. Thus, even when the locking pin 21, 31 is used as a component of a zipper slider in a product where the entire product is conceptually pure black, the locking pin 21, 31 does not stand out and does not give a different impression. In some examples, there is one instance where the difference (ΔL*) in brightness L* between the slider body 23, 33 and the locking pin 21, 31 exceeds the value 6.3, resulting in a slightly brighter brightness difference. However, since the difference (Δa*) in the value of a* is kept in a low range of less than 2.7, there is no discomfort such as, for example,that the color appears reddish-brown depending on the angle of reflection of light.

[0037] In particular, the difference (ΔL*) in brightness L* between the locking pin 21, 31 made of nickel-based austenitic stainless steel in Examples 1-1 to 1-15 and the slide body 23, 33 is kept within a low range of 4.34 ≤ ΔL* ≤ 6.79. The “color difference Δa* from the body” and the “color difference Δb* from the body” are also kept low within an acceptable range, and in particular, the difference (Δa*) in the value of a* is kept low, within a range of 1.11 ≤ Δa* ≤ 2.47. This makes it less likely that there is a significant difference in the appearance of the black colors of the two components. Furthermore, the absolute value of the brightness L* satisfies the condition 31.70 ≤ L* ≤ 34.16, and the value of a* and the value of b* satisfy 0.369 ≤ a* ≤ 1.736 and -2.428 ≤ b* ≤ 0.466 respectively.Therefore, the black color of the locking pin 21, 31 is a black color in an area that has a lower reflectance and a higher absorption for visible light than the same black color that is referred to as pure black, so that even when the locking pin 21, 31 is used as a component of a zipper slider in a product where the entire product is conceptually pure black, the locking pin 21, 31 does not stand out and does not give a different impression.

[0038] In particular, the difference (ΔL*) in brightness L* between the locking pin 21, 31 made of manganese-based austenitic stainless steel in Examples 2-1 to 2-15 and the slide body 23, 33 is kept within a low range of 5.68 ≤ ΔL* ≤ 8.54. The “color difference Δa* from the body” and the “color difference Δb* from the body” are also kept low within an acceptable range, and in particular, the difference (Δa*) in the value of a* is kept low, within a range of 0.03 ≤ Δa* ≤ 2.67. This makes it less likely that there is a significant difference in the appearance of the black colors of the two components. Furthermore, the absolute value of the brightness L* satisfies the condition 33.04 ≤ L* ≤ 35.90, and the value of a* and the value of b* satisfy -0.708 ≤ a* ≤ 1.929 and -2.388 ≤ b* ≤ -1.495 respectively.Therefore, the black color of the locking pin 21, 31 is a black color in an area that has a lower reflectance and a higher absorption for visible light than the same black color that is referred to as pure black, so that even when the locking pin 21, 31 is used as a component of a zipper slider in a product where the entire product is conceptually pure black, the locking pin 21, 31 does not stand out and does not give a different impression.

[0039] Similar to the locking pin 21, 31, the test pieces (test pieces in the shape of a zipper dome link) made of ferritic stainless steel (SUS430) from Example 3-1 to Example 3-15 also exhibit a difference (ΔL*) in brightness L* that is kept within a low range of 2.31 ≤ ΔL* ≤ 8.94. The “color difference Δa* from the body” and the “color difference Δb* from the body” are also kept low within an acceptable range, and in particular, the difference (Δa*) in the value of a* is kept low, within a range of 0.11 ≤ Δa* ≤ 1.49. This makes it less likely that there is a significant difference in the appearance of the black colors of the two components. Furthermore, the absolute value of the brightness L* satisfies the condition 29.67 ≤ L* ≤ 36.24, and the value of a* and the value of b* satisfy the conditions -0.63 ≤ a* ≤ 0.76 and 0.42 ≤ b* ≤ 1.22, respectively.By using not only the sliders 20, 30, but also the zipper dome link from Example 3-1 to Example 3-15 in a product where the entire product is conceptually all black, the links of the zipper no longer stand out and do not give a different impression, and the zipper as a whole can give a uniform impression of black.

[0040] In contrast, a similar color measurement was performed on a comparison example of a locking pin that had been blackened by chemical conversion treatment, but where the degree of blackening was insufficient (that is, a comparison example with a black color whose reflectance for visible light was not low enough and whose absorptivity for visible light was not high enough). The results are shown below. [Table 4] L* a* b* Difference ΔL* in the brightness of the body Color difference Δa* from the body Color difference Δb* from the body Comparative example 1 33,71 4,6 -0 6,35 5,40 0,26 Comparative example 2 43,48 18,89 10,58 16,1 19,6 11,0

[0041] The locking pin of comparison example 1 in Table 4 has a black appearance that, compared to those of examples 1-1 to 2-15 above, is slightly reddish-black and appears reddish-brown depending on the angle of reflection of light. The locking pin of comparison example 1 exhibits a difference (ΔL*) in brightness L* from the slide body 23, 33 of ΔL* = 6.35, which is somewhat high, and the color difference Δa* from the body is 5.40, which is also high. Therefore, the impression arises that there is a large difference in the appearance of the black color compared to the slide body. Furthermore, the absolute value of brightness L* satisfies the condition L* = 33.71, and the values ​​of a* and b* satisfy the conditions a* = 4.67 and b* = -0.16, respectively.Therefore, the black color of the locking pin is not a black color in an area that has a lower reflectance and a higher absorption for visible light than the same black color that is referred to as pure black, and when the locking pin is used as a component of a zipper slider in a product where the entire product is conceptually pure black, the locking pin stands out and gives a different impression.

[0042] The locking pin of comparison example 2 in Table 4 has an appearance that is more brown than black and also appears brown depending on the angle of reflection of light. The locking pin of comparison example 2 exhibits an extremely high difference (ΔL*) in brightness L* from the slide body 23, 33, with ΔL* = 16.1, and the color difference Δa* from the body is 19.6, which is also high. Therefore, the impression arises that there is a large difference in the appearance of the black color compared to the slide body. Furthermore, the absolute value of brightness L* satisfies the condition L* = 43.48, and the values ​​of a* and b* satisfy the conditions a* = 18.89 and b* = 10.58, respectively.Therefore, the color of the locking pin is more brown than black, and if the locking pin is used as a component of a zipper slider in a product where the entire product is conceptually all black, the locking pin stands out and gives a different impression.

[0043] In contrast, the sliders 20, 30 of the present invention have the design described above. Therefore, even when the locking pin 21, 31, which has undergone chemical conversion to black, is used as a component of a zipper slider in a product where the entire product is conceptually all black, the impression is not created that only the locking pin 21, 31 stands out in a different color. Furthermore, if a similar black oxide layer is also provided on the stainless steel coupling element, the zipper as a whole can convey a uniform black appearance.

[0044] Next, the state of the oxide layer thickness, which in the embodiments of the present invention is formed on the surface of the locking pin 21, 31 or the test piece (test piece in the shape of a zipper coupling link), is described with reference to Fig. 6 to 23 described.

[0045] Fig. Figures 6 to 17 are graphenes showing the results of a distribution state of metal elements contained in the black oxide layer 53, which is formed on the surface of the locking pin 21, 31 according to the embodiment of the present invention, analyzed in a depth direction by Auger electron spectroscopy. Fig.Figures 18 to 23 are graphenes showing the results of a distribution state of metal elements contained in the black oxide layer 53, which in the embodiment of the present invention is formed on a surface of the test piece (test piece in the shape of a zipper dome link), analyzed in the depth direction by Auger electron spectroscopy.

[0046] First, Fig. 6 to 11 described. Fig. Figures 6 to 11 show the results of the analysis of the locking pins 21, 31 according to the embodiment of the invention, which are made of a nickel-based austenitic stainless steel with a nickel content of 10% to 14%, as shown in Examples 1-1 to 1-15 in Table 1 above. For the sake of simplicity, the Fig. The 6 analyzed example samples are designated as examples 1-16, which are in Fig. The 7 analyzed example samples are referred to as example 1-17, which are in Fig. The 8 analyzed example samples are referred to as example 1-18, which are in Fig. The 9 analyzed example samples are referred to as example 1-19, which are in Fig. The 10 analyzed sample samples are referred to as sample 1-20, and those in Fig. The 11th analyzed example sample is designated as Example 1-21. To explain in detail the relationship between the example samples of Examples 1-1 to 1-15 shown in Table 1 and the example samples of Examples 1-16 to 1-21, for which layer thickness data were obtained by Auger electron spectroscopy, Examples 1-1 to 1-5 in Table 1 and Example 1-16 ( Fig. 6) and example 1-17 ( Fig.7), for which layer thickness data were obtained by Auger electron spectroscopy, example samples from a group that underwent the chemical transformation treatment as the same production batch. That is, when a small component such as the locking pin undergoes a chemical transformation treatment, several hundred locking pins are subjected to the chemical transformation treatment at once, and from the several hundred production batches that undergo the chemical transformation treatment at once, seven locking pins, designated as Example 1-1, Example 1-2, Example 1-3, Example 1-4 and Example 1-5, which are shown in Table 1, as well as Example 1-16 ( Fig. 6) and example 1-17 ( Fig. 7), for which the layer thickness data were obtained using Auger electron spectroscopy, were randomly removed for the purpose of obtaining measurement data.

[0047] Similarly, seven locking pins, designated as Example 1-6, Example 1-7, Example 1-8, Example 1-9 and Example 1-10, which are shown in Table 1, as well as Example 1-18 ( Fig. 8) and example 1-19 ( Fig. 9), for which the layer thickness data were obtained by Auger electron spectroscopy, belong to a group that underwent the chemical transformation treatment as the same production batch. Similarly, seven locking pins, designated as Example 1-11, Example 1-12, Example 1-13, Example 1-14 and Example 1-15, which are shown in Table 1, as well as Example 1-20 ( Fig. 10) and example 1-21 ( Fig. 11), for which the layer thickness data were obtained using Auger electron spectroscopy, to a group which was subjected to the chemical conversion treatment as the same production batch.

[0048] It will now Fig. 6 described. Fig.Figure 6 is a graph showing the change in the proportion of each metallic element in the thickness direction of the oxide layer of the locking pin 21. The thickness of the oxide layer can be estimated by observing the changes in the distribution of oxygen (O) along with the constituent elements iron (Fe), manganese (Mn), chromium (Cr), nickel (Ni), carbon (C), and silicon (Si) contained in the stainless steel as the base material. For the sake of simplicity, in this description, the thickness in the depth direction up to the point where the amount of oxygen formed on the sample is 50% of the amount (maximum value) near the surface is defined as the thickness of the oxide layer (hereinafter referred to simply as "thickness of the oxide layer" or "layer thickness"). For example, in Fig.6. The maximum value of the oxygen quantity near the surface formed on the sample on the vertical axis (intensity) is approximately 3500, and the depth at which 50% of this value, i.e. 1750, is reached is 340 nm and is taken as the thickness of the oxide layer.

[0049] That means the thickness of the oxide layer of example 1-16 is 340 nm.

[0050] Similarly, the thickness of the oxide layer is determined by the thickness of the oxide layer of the in Fig. In example 7, 1-17 equals 320 nm. The thickness of the oxide layer of the in Fig. The thickness of the oxide layer in the example shown is 530 nm. Fig. In example 1-19 shown in Figure 9, the thickness is 480 nm. Fig. The thickness of the oxide layer shown in example 10 is 1260 nm. Fig. Example 1-21 shown in 11 is 1010 nm.

[0051] The distribution range of the oxide layer thickness of the six example samples, Example 1-16 to Example 1-21, is 320 nm or more and 1260 nm or less.

[0052] Next will Fig. Described in sections 12 to 17. Fig. 12 to Fig. Figure 17 shows the results of the analysis of the locking pins 21, 31 according to the embodiment of the present invention, which are made of a manganese-based austenitic stainless steel with a manganese content of 13% to 17%, as shown in Examples 2-1 to 2-15 in Table 2 above. For the sake of simplicity, the Fig. 12 analyzed example samples, designated as example 2-16, which are in Fig. The 13th analyzed example sample is referred to as example 2-17, which is in Fig. The 14 analyzed example sample is referred to as example 2-18, which is in Fig. The 15 analyzed example sample is referred to as example 2-19, which is in Fig.The 16 analyzed example sample is referred to as example 2-20, and the one in Fig. The 16th analyzed example sample is designated as Example 2-21. To explain in detail the relationship between the example samples of Examples 2-1 to 2-15 shown in Table 2 and the example samples of Examples 2-16 to 2-21, for which layer thickness data were obtained by Auger electron spectroscopy, Examples 2-1 to 2-5 in Table 2 and Example 2-16 ( Fig. 12) and example 2-17 ( Fig.13), for which layer thickness data were obtained by Auger electron spectroscopy, example samples from a group that underwent the chemical transformation treatment as the same production batch. That is, when a small component such as the locking pin undergoes a chemical transformation treatment, several hundred locking pins are subjected to the chemical transformation treatment at once, and from the several hundred production batches that undergo the chemical transformation treatment at once, seven locking pins, designated as Example 2-1, Example 2-2, Example 2-3, Example 2-4 and Example 2-5, which are shown in Table 2, as well as Example 2-16 ( Fig. 12) and Example 2-17 ( Fig. 13), for which the layer thickness data were obtained using Auger electron spectroscopy, were randomly removed for the purpose of obtaining measurement data.

[0053] Similarly, seven locking pins, designated as Example 2-6, Example 2-7, Example 2-8, Example 2-9 and Example 2-10, which are shown in Table 2, as well as Example 2-18 ( Fig. 14) and Example 2-19 ( Fig. 15), for which the layer thickness data were obtained by Auger electron spectroscopy, belong to a group that underwent the chemical transformation treatment as the same production batch. Similarly, seven locking pins, designated as Example 2-11, Example 2-12, Example 2-13, Example 2-14 and Example 2-15, which are shown in Table 2, as well as Example 2-20 ( Fig. 16) and Example 2-21 ( Fig. 17), for which the layer thickness data were obtained by Auger electron spectroscopy, to a group which was subjected to the chemical conversion treatment as the same production batch.

[0054] The definition derived from the measurement data in Fig.The thickness of the oxide layer, as read from 12 to 17, corresponds to that measured with reference to Fig. 6 described method. That is, in Fig. 12. The maximum value of the amount of oxygen near the surface formed on the sample is approximately 3750 on the vertical axis (intensity), and the depth at which 50% of this value, i.e. 1875, is reached is 440 nm and is taken as the thickness of the oxide layer.

[0055] That means the thickness of the oxide layer of example 2-16 is 440 nm.

[0056] Similarly, the thickness of the oxide layer is determined by the thickness of the oxide layer of the in Fig. Example 13, 2-17, is equal to 570 nm. The thickness of the oxide layer in Fig. In example 2-18 shown in Figure 14, the wavelength is 840 nm. The thickness of the oxide layer in Fig. In example 2-19 shown in Figure 15, the wavelength is 860 nm. The thickness of the oxide layer in Fig. Example 2-20 shown in 16 is 1870 nm. The thickness of the oxide layer of the in Fig.Example 2-21 shown in 15 is 1830 nm.

[0057] The distribution range of the oxide layer thickness of the six example samples, Example 2-16 to Example 2-21, is 440 nm or more and 1870 nm or less.

[0058] On the other hand, the following will refer to Fig. 18 to 21 describe a comparative example in the same way as in the embodiments described above, in which the thickness of the oxide layer is insufficient to adequately reduce the reflection of visible light to almost completely black.

[0059] Fig. 18 and Fig. Figure 19 shows the results of the Auger electron spectroscopy analysis, performed in the same manner as in the examples above, on a sample taken from the locking pins that underwent chemical transformation treatment in the same production batch as Comparative Example 1. For simplicity, the Fig. Sample 18 analyzed, designated as comparison example 1-2, and the in Fig. Sample 19 analyzed is referred to as Comparative Example 1-3. When an estimated value of the layer thickness is obtained by analyzing Comparative Example 1-2 and Comparative Example 1-3 using Auger electron spectroscopy in the same manner as described above, it is evident that the thickness of the oxide layer in Comparative Example 1-2 is approximately 2020 nm and the thickness of the oxide layer in Comparative Example 1-3 is approximately 2300 nm. That is, it is evident that the layer thickness of Comparative Example 1 was too thick compared to the layer thickness distribution range of the examples of the present invention.

[0060] Fig. 20 and Fig.Figure 21 shows the results of the Auger electron spectroscopy analysis, performed in the same manner as in the examples above, on a sample taken from the locking pins that underwent the chemical conversion treatment in the same production batch as Comparative Example 2. For simplicity, the Fig. Sample 20 analyzed, designated as comparison example 2-2, and the in Fig.The 21 analyzed sample is referred to as Comparative Example 2-3. When an estimated value of the layer thickness is obtained by analyzing Comparative Example 2-2 and Comparative Example 2-3 using Auger electron spectroscopy in the same manner as described above, it is evident that the thickness of the oxide layer in Comparative Example 2-2 is approximately 40 nm and the thickness of the oxide layer in Comparative Example 2-3 is approximately 60 nm. That is, it is evident that the layer thickness of Comparative Example 2 was too thin compared to the layer thickness distribution range of the examples of the present invention.

[0061] Furthermore, the locking pin was manufactured from a stainless steel containing 10% or more by weight and 14% or less by weight of nickel, as in Comparative Example 2. However, another sample, which had undergone a chemical transformation treatment as a production batch different from that of Comparative Example 2, was also subjected to additional analysis by Auger electron spectroscopy. This is referred to as Comparative Example 3.

[0062] In comparative example 3, the black color appears slightly reddish-black and brown depending on the angle of reflection of light, and it cannot be evaluated as a black color in an area that has a lower reflectance and a higher absorption for visible light, which is called pure black. Fig.Figure 22 shows the results of the Auger electron spectroscopy analysis of comparison example 3 in the same manner as described above. Based on Fig. In example 22, the layer thickness was estimated in the same way as above, and the thickness of the oxide layer was approximately 2020 nm. That is, it is evident that the layer thickness of Comparative Example 3 was too thick compared to the layer thickness distribution range of the examples of the present invention.

[0063] The analysis results of the examples and comparison examples described above revealed that when the oxide layer thickness was greater than 2000 nm, as in comparison example 1, there was a tendency towards light reflection. In this case, the brightness L* was low, but the value of a* was high, resulting in a lighter reddish-black color compared to the examples and a reddish-brown color depending on the angle of reflection. Conversely, when the oxide layer thickness was less than 100 nm, as in comparison example 2, the brightness L* was too high (too bright), and the values ​​of a* and b* were also high, leading to the reflection of colored light. Compared to the examples, the appearance was more brown than black, and the appearance also appeared brown depending on the angle of reflection.From comparative example 3, it was also found that when the thickness of the oxide layer was greater than 2000 nm, the black color became slightly reddish-black in appearance.

[0064] From the results of the above comparative examples, it was determined that the oxide layer thickness is necessarily greater than 100 nm and less than 2000 nm. From the results of the above examples, it was determined that the oxide layer thickness is preferably 320 nm or more and 1870 nm or less.

[0065] It is also evident that when comparing the distribution of the numerical range suitable for the layer thickness of the locking pins made of the nickel-based stainless steel shown in Examples 1-16 to 1-21 with the distribution of the numerical range suitable for the layer thickness of the locking pins made of the manganese-based stainless steel shown in Examples 2-16 to 2-21, the numerical range suitable for the nickel-based material is shifted towards a slightly smaller layer thickness than for the manganese-based material. That is, if the stainless steel of the locking pin 21, 31 is a stainless steel containing 10 wt% or more and 14 wt% or less nickel, the thickness of the oxide layer on the surface of the locking pin 21, 31 is preferably 320 nm or more and 1260 nm or less.And if the stainless steel of the locking pin 21, 31 is a stainless steel containing 13 wt. percent or more and 17 wt. percent or less manganese, the thickness of the oxide layer on the surface of the locking pin 21, 31 is preferably 440 nm or more and 1870 nm or less.

[0066] In general, the formation of a black oxide layer on stainless steel through chemical conversion treatment is related to the fact that the layer thickness increases with increasing immersion time in a chemical conversion solution (such as a chromic acid solution, a caustic soda solution, or the like). Therefore, if, as described above, the appropriate range of layer thickness is known, the appropriate range of immersion time in the chemical conversion solution can be easily derived, and the technical knowledge described above is advantageous for improving the efficiency of the manufacturing process.

[0067] Next, the layer thickness of a test piece (a test piece in the shape of a zipper coupling link), which was not a locking pin (the material is a ferritic stainless steel (SUS430)), was analyzed in the same way, and the results are presented with reference to Fig. Described in sections 23 to 28.

[0068] Ferritic stainless steel is an alloy of iron and chromium and contains no nickel, which makes it susceptible to oxidation (rusting). On the other hand, ferritic stainless steel has the advantage of being less prone to work hardening and easier to machine than austenitic stainless steel, making it a suitable material for high-speed components such as forgings, like a coupling link. While the circumstances differ from those of locking pins, where austenitic stainless steel is advantageous, achieving a uniform black appearance for the entire zipper requires a thorough analysis and investigation of the tendency for blackening due to surface treatment of the coupling link, along with the tendency of the locking pin and slider to blacken.

[0069] Fig. Figures 23 to 28 show the results of the analysis of test pieces (test pieces in the shape of a zipper dome link) made of ferritic stainless steel (SUS430), as in Examples 3-1 to 3-15 in Table 3 above. For simplicity, the Fig. 23 analyzed example samples, designated as example 3-16, which are in Fig. The 24 analyzed example sample is referred to as example 3-17, which is in Fig. The 25 analyzed example sample is referred to as example 3-18, which is in Fig. The 26 analyzed example sample is referred to as example 3-19, which is in Fig. The 27 analyzed example sample is referred to as example 3-20, and the one in Fig.The 28 analyzed example sample is designated as Example 3-21. To explain in detail the relationship between the example samples of Examples 3-1 to 3-15 shown in Table 3 and the example samples of Examples 3-16 to 3-21, for which layer thickness data were obtained by Auger electron spectroscopy, Examples 3-1 to 3-5 in Table 3 and Example 3-16 ( Fig. 23) and example 3-17 ( Fig.24), for which layer thickness data were obtained by Auger electron spectroscopy, example samples from a group that underwent the chemical transformation treatment as the same production batch. That is, when a small component such as the locking pin undergoes a chemical transformation treatment, several hundred locking pins are subjected to the chemical transformation treatment at once, and from the several hundred production batches that undergo the chemical transformation treatment at once, seven locking pins, designated as Example 3-1, Example 3-2, Example 3-3, Example 3-4 and Example 3-5, which are shown in Table 3, as well as Example 3-16 ( Fig. 23) and Example 3-17 ( Fig. 24), for which the layer thickness data were obtained using Auger electron spectroscopy, were randomly removed for the purpose of obtaining measurement data.

[0070] Similarly, seven locking pins, designated as Example 3-6, Example 3-7, Example 3-8, Example 3-9 and Example 3-10, which are shown in Table 3, as well as Example 3-18 ( Fig. 25) and Example 3-19 ( Fig. 26), for which the layer thickness data were obtained by Auger electron spectroscopy, belong to a group that underwent the chemical transformation treatment as the same production batch. Similarly, seven locking pins, designated as Example 3-11, Example 3-12, Example 3-13, Example 3-14 and Example 3-15, which are shown in Table 3, as well as Example 3-20 ( Fig. 27) and Example 3-21 ( Fig. 28), for which the layer thickness data were obtained by Auger electron spectroscopy, to a group which was subjected to the chemical conversion treatment as the same production batch.

[0071] The definition derived from the measurement data in Fig.The thickness of the oxide layer read from 23 to 28 corresponds to that measured with reference to Fig. 6 described method. That is, in Fig. 23 The maximum value of the amount of oxygen near the surface formed on the sample is approximately 4300 on the vertical axis (intensity), and the depth at which 50% of this value, i.e. 2150, is reached is 1010 nm and is taken as the thickness of the oxide layer.

[0072] That means the thickness of the oxide layer of example 3-16 is 1010 nm.

[0073] Similarly, the thickness of the oxide layer is determined by the thickness of the oxide layer of the in Fig. Example 24 shows 3-17, which is equal to 1070 nm. The thickness of the oxide layer of the in Fig. Example 3-18 shown in 25 is 1620 nm. The thickness of the oxide layer of the in Fig. Example 3-19 shown in Figure 26 is 1470 nm. The thickness of the oxide layer of the in Fig. Example 3-20 shown in 27 is 2190 nm. The thickness of the oxide layer in Fig. In example 3-21, shown in Figure 28, the thickness is 2500 nm or more, which is above the range measurable by the instrument. Therefore, the layer thickness cannot be obtained using the estimation method described above. However, it can be deduced that the thickness is approximately 2600 nm or more and 2800 nm or less. The mean of these values ​​is then taken, and 2700 nm is set as the estimated value for the layer thickness.

[0074] The distribution range of the oxide layer thickness of the six example samples, Example 3-16 to Example 3-21, is 1010 nm or more and 2700 nm or less.

[0075] The shape of the dome member is roughly a hexahedron with opposing parallel planes, and these planes likely overlap during the surface treatment with the chemical solution. Since the dye does not flow easily over the overlapping surfaces, the layer thickness growth on these surfaces is slowed. Conversely, because the locking pin is not a hexahedron, the dye flows readily over its entire surface. Therefore, to achieve uniform dyeing (chemical conversion treatment) on the dome member, the treatment time must be longer than for the locking pin, resulting in a thicker oxide layer on the surface.On the other hand, since the layer thickness on the surface of the locking pin increases almost uniformly across the entire surface, it can be uniformly colored in a short time. Furthermore, because ferritic stainless steel contains no nickel, it oxidizes more readily than austenitic stainless steel, and the rate of layer thickness growth tends to increase with surface treatment. For these reasons, the oxide layer thickness of the coupling element made of ferritic stainless steel tends to be greater than the oxide layer thickness of the locking pin made of austenitic stainless steel.In this respect, it is important to comprehensively analyze and investigate the tendency to blacken due to surface treatment of the dome member, together with the tendency to blacken the locking pin and slider, in order to achieve a uniform appearance in black for the entire zipper, even though the surface treatment of the dome member differs from the surface treatment of the locking pin.

[0076] From the results of the above Fig.23 to 28 and the color measurement data shown in Table 3, it was found that when the thickness of the oxide layer for the test piece (test piece in the shape of a zipper dome link) made of ferritic stainless steel (SUS430) was adjusted to 1010 nm or more and 2700 nm or less, the black color becomes a black color in a range that has a lower reflectance and a higher absorption for visible light than the same black color, which is referred to as pure black.It was determined that by using a ferritic stainless steel (SUS430) not only for the slider 20, 30, but also for the zipper dome link, with a layer thickness in the preferred numerical range described above, in a product where the entire product is conceptually pure black, no section of the zipper links stands out and gives a different impression, and that the zipper as a whole can give a uniform impression of black.

[0077] The present invention is not limited to the embodiments disclosed above, but it is also possible to use techniques that a person skilled in the art would recognize as essentially equivalent to the technical features described in the embodiments of the present invention, or techniques that have the same effects as the technical features, as alternative techniques, or to add such techniques in addition. Furthermore, it is also possible to recombine and implement characteristic designs of the above embodiments.

[0078] Furthermore, throughout this description, parts described in the drawings by reference numerals are described as components that are at least required in every embodiment of the present invention, and they do not mean that the present invention consists only of the parts described in the drawings by reference numerals.

[0079] Furthermore, the numerical values ​​given in the text of this description are transcribed, analyzed and compared based on the numerical values ​​in the table listed in this description, and if there is any discrepancy in the correspondence of the numerical values, the numerical values ​​entered in the tables are, in principle, assumed to be more accurate. REFERENCE MARK LIST 20, 30 sliders 21, 31 Locking pin 23, 33 Slide body 25, 35 pull piece QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] WO 2016 / 092637A1

[0003] JP 2002-010808A

[0003] Cited non-patent literature

[0000] JIS Z8781-4 (2013 [0012, 0013, 0014, 0015, 0017, 0030]

Claims

[1] Zipper slider (20, 30) comprising the following: a sliding body (23, 33); a pull piece (25, 35); and a locking pin (21, 31), wherein the locking pin (21, 31) is made of stainless steel, wherein a black oxide layer is formed on a surface of the locking pin (21, 31), and wherein the surface of the locking pin (21, 31) has a brightness L* that satisfies 31.70 ≤ L* ≤ 35.90 and an a* value that satisfies -0.708 ≤ a* ≤ 1.929, where the brightness L* and the a* value correspond to definitions in a CIELAB color space defined in JIS Z8781-4 (2013). [2] Zipper slider according to claim 1, wherein the surface of the locking pin (21, 31) has a b* value which satisfies -2.428 ≤ b* ≤ 0.466, wherein the b* value corresponds to a definition in the CIELAB color space defined in JIS Z8781-4 (2013). [3] Zipper slider according to claim 1, wherein the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 10 wt% to 14 wt% nickel, and wherein the surface of the locking pin (21, 31) has a brightness L* that satisfies 31.70 ≤ L* ≤ 34.16, an a* value that satisfies 0.369 ≤ a* ≤ 1.736, and a b* value that satisfies -2.428 ≤ b* ≤ 0.466, wherein the brightness L*, the a* value, and the b* value correspond to definitions in the CIELAB color space defined in JIS Z8781-4 (2013). [4] Zipper slider according to claim 1, wherein the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 13 wt% to 17 wt% manganese, and wherein the surface of the locking pin (21, 31) has a brightness L* that satisfies 33.04 ≤ L* ≤ 35.90, an a* value that satisfies -0.708 ≤ a* ≤ 1.929, and a b* value that satisfies -2.388 ≤ b* ≤ -1.495, wherein the brightness L*, the a* value and the b* value correspond to definitions in the CIELAB color space defined in JIS Z8781-4 (2013). [5] Zipper slider according to claim 1 or 2, wherein the slider body (23, 33) is black and where, according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013): a difference ΔL* between the brightness L* of the slide body (23, 33) and the brightness L* of the locking pin (21, 31) satisfies the condition ΔL* ≤ 8.54, and a difference Δa* between the a* value of the slide body (23, 33) and the a* value of the locking pin (21, 31) satisfies the condition 0.03 ≤ Δa* ≤ 2.

67. [6] Zipper slider according to claim 3, wherein the slider body (23, 33) is black and where, according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013): a difference ΔL* between the brightness L* of the slide body (23, 33) and the brightness L* of the locking pin (21, 31) satisfies the condition ΔL* ≤ 6.79, and a difference Δa* between the a* value of the slide body (23, 33) and the a* value of the locking pin (21, 31) satisfies the condition 1.11 ≤ Δa* ≤ 2.

47. [7] Zipper slider according to claim 4, wherein the slider body (23, 33) is black and where according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013) a difference ΔL* between the brightness L* of the slide body (23, 33) and the brightness L* of the locking pin (21, 31) satisfies the condition ΔL* ≤ 8.54, and a difference Δa* between the a* value of the slide body (23, 33) and the a* value of the locking pin (21, 31) satisfies the condition 0.03 ≤ Δa* ≤ 2.

67. [8] Zipper comprising the following: the zipper slider according to any one of claims 1 to 4, wherein a link of the zipper is made of ferritic stainless steel and the link has a brightness L* that satisfies 29.67 ≤ L* ≤ 36.24, an a* value that satisfies -0.63 ≤ a* ≤ 0.76, and a b* value that satisfies 0.42 ≤ b* ≤ 1.22, wherein the brightness L*, the a* value and the b* value correspond to definitions in the CIELAB color space defined in JIS Z8781-4 (2013). [9] Zipper according to claim 8: wherein the slider body (23, 33) is black and where, according to the definitions in the CIELAB color space defined in JIS Z8781-4 (2013), a difference ΔL* between the brightness L* of the element and the brightness L* of the slider body (23, 33) satisfies the condition ΔL* ≤ 8.94 and a difference Δa* between their a* values ​​satisfies the condition 0.11 ≤ Δa* ≤ 1.

49. [10] Zipper slider according to claim 1 or 2, wherein the oxide layer on the surface of the locking pin (21, 31) has a thickness of 320 nm or more and 1870 nm or less. [11] Zipper slider according to one of claims 1, 3 or 6, wherein the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 10 wt% or more and 14 wt% or less nickel, and the thickness of the oxide layer on the surface of the locking pin (21, 31) is 320 nm or more and 1260 nm or less. [12] Zipper slider according to one of claims 1, 4 or 7, wherein the stainless steel for the locking pin (21, 31) is an austenitic stainless steel containing 13 wt% or more and 17 wt% or less manganese, and the thickness of the oxide layer on the surface of the locking pin (21, 31) is 440 nm or more and 1870 nm or less. [13] Zipper according to claim 8, wherein the thickness of an oxide layer on the link of the zipper is 1010 nm or more and 2700 nm or less.

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