WO2017006402A1 - Fastener chain with rows of copper alloy elements and slide fastener - Google Patents

Abstract

Provided is a fastener chain with rows of copper alloy elements having different colors. The fastener chain can be produced at low cost and the copper alloy elements are colored by a technique other than plating. The fastener chain is provided with: a pair of rows of copper alloy elements (103) which are engaged with each other; and a pair of fastener tapes (101) each having one side edge to which either of the rows of elements (103) is attached. The exposed surfaces of the elements (103) have oxide coatings having different copper (I) oxide contents and copper (II) oxide contents in order to cause a variation in the color of the elements (103) along the length of the rows.

Description

Fastener chain and slide fastener with rows of copper alloy elements

The present invention relates to a fastener chain having a row of copper alloy elements. The present invention also relates to a slide fastener provided with the fastener chain.

Conventionally, elements using a metal material for an element which is an engaging part of a slide fastener are known, and among those metal materials, those using a copper alloy as a material are often used. An example of a procedure for planting a copper alloy element on a fastener tape will be described below. As shown in FIG. 1, after forming a deformed wire 10 having a substantially Y-shaped cross section corresponding to the shape of the element through casting, wire drawing, recrystallization annealing, and cold working, the deformed wire 10 is formed for each predetermined dimension. A number of Y-shaped members 20 are obtained by sequentially cutting. Next, as shown in FIG. 2, the element 30 is produced by press-molding the meshing recess 22 and the meshing projection 23 on the upper and lower surfaces of the head 21 of the cut Y-shaped member 20 by a forming punch. The element 30 manufactured in this way is sequentially planted and fixed at regular intervals along the longitudinal side edge of the fastener tape 40 by caulking both the leg portions 24a and 24b.

Such copper alloy elements have been colored by plating for the purpose of improving functionality and design. In Japanese Patent Application Laid-Open No. 2001-8714, a plating process is performed on the surface of a long body made of a metal or an alloy to form a film having a film thickness of 0.001 to 10 μm, and this is cut into constituent members. A method of manufacturing an adherend with constituent members, which is mounted on a kimono, is disclosed. Japanese Patent Application Laid-Open No. 2003-180410 discloses a method for forming a film on an element by combining electrolytic plating and electroless plating. In this method, electrolytic plating is performed in the state of a deformed wire having a substantially Y-shaped cross section for producing an element, electroless plating is performed after the element is attached to the fastener tape, and plating treatment is performed on all outer surfaces of the element. It is a technology to apply.

In addition, a design is known in which metallic elements having different hues are implanted in a fastener tape in a predetermined arrangement pattern to give various hues to the element rows (eg, Chinese Design No. 302356575, Chinese Design No. 2). No. 30277555). Such an array of elements having a variety of colors is one of a technique using a parts feeder that can select elements according to hue (Japanese Patent Publication No. 7-49002, WO2014 / 077686), and a plurality of wires having different colors. Has been manufactured by using a technique (WO2015 / 049767) in which element elements are formed by cutting and forming element elements by cutting at a predetermined pitch and fixing them to a fastener tape.

JP 2001-8714 A JP 2003-180410 A Chinese Design No. 302356575 Chinese Design No. 30277555 Japanese Patent Publication No. 7-49002 WO2014 / 077686 WO2015 / 049767

In the element coloring technique described in Japanese Patent Application Laid-Open No. 2001-8714, there is a problem that the cut surface is not colored because the wire is cut after plating and is embedded in the fastener tape. In the element coloring technique described in Japanese Patent Laid-Open No. 2003-180410, it is possible to plate all outer surfaces of an element by electroless plating after cutting the wire after electrolytic plating and planting it on a fastener tape. However, there is a problem that a two-step plating process is required, and a coating formed by electroless plating is inferior in design to a coating formed by electrolytic plating.

Further, when arranging metal elements having different hues, a technology using a parts feeder that can select elements according to hues (Japanese Patent Publication No. 7-49002, WO 2014/076786) has a complicated mechanism. A feeder is required, and elements having a large number of hues must be prepared in advance, which complicates the manufacturing procedure and increases the manufacturing cost. In the case of a technique (WO2015 / 049767) in which one element is selected from a plurality of wires having different colors and cut at a predetermined pitch to form an element element and fixed to a fastener tape (WO2015 / 049767), there is an advantage of reducing the manufacturing cost. However, there is a problem that the cut surface is not colored.

The present invention was created in the background of the above circumstances, and is a fastener chain having a row of copper alloy elements whose hue changes, which can be manufactured at low cost, and is a copper alloy by a method different from plating. An object is to provide a fastener chain in which colored elements are colored.

If the metal fasteners are colored by plating after the element rows are planted on the fastener tape, the plating solution penetrates into the fastener tape. In order not to leave this, the cleaning process must be performed many times in a bath mixed with a cleaning agent, and depending on the material of the fastener tape, there is a problem that the texture, texture, etc. are impaired. For this reason, the coloring of the metal fastener by plating is often performed before the fastener tape is implanted.

The present inventor has intensively studied in order to solve the above-mentioned problems. As a result, attention is paid to the fact that the hue of copper oxide changes greatly depending on the oxidation number. It has been found that it is effective to arrange elements having different constituent ratios of cuprous oxide (Cu ₂ O) and cupric oxide (CuO) mainly for the copper oxide constituting the metal oxide. An oxide film can be formed on the element surface by an anodic oxidation method. When the anodizing method is used, even if coloring is performed after the rows of elements are installed on the fastener tape, the electrolyte solution does not contain substances that are highly toxic to the human body. Thorough cleaning can be performed and problems such as plating do not occur. Further, the hue change of the element can be achieved only by changing the anodic oxidation conditions, and it is possible to easily create a wide range of hues with the help of the large hue change due to the oxidation number of copper oxide. The present invention has been completed based on this knowledge.

In one aspect, the present invention is a fastener chain comprising a pair of elements made of copper alloy that engage with each other and a pair of fastener tapes each attached to the element array along one side edge, Each of the exposed surfaces of the elements has an oxide film having different contents of cuprous oxide and cupric oxide, so that the hue exhibited by each of the elements changes in the length direction of the row.

In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the largest a ^* value of the exposed surface The difference of the a ^* value from the element having the smallest a ^* value on the exposed surface is 10 or more.

In another embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the b ^* value of the exposed surface is the largest. The difference in b ^* value between the element and the element with the smallest b ^* value on the exposed surface is 20 or more.

In yet another embodiment of the fastener chain according to the present invention, in the CIELAB color space defined by JIS Z8781-4 (2013), among the elements constituting the row, the a ^* value of the exposed surface is the largest. a ^* value of greater elements is not less than 10, a ^* value of the smallest element of a ^* value of the exposed surface is 5 or less.

In yet another embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the b ^* value of the exposed surface is the highest. b ^* value of greater elements is not less than 20, the b ^* value of the smallest element of the b ^* value of the exposed surface is 10 or less.

In still another embodiment of the fastener chain according to the present invention, in the elements constituting the row, the component content of cuprous oxide in the oxide film is higher than the component content of cupric oxide. And at least one element in which the component content of cupric oxide in the oxide film is greater than the component content of cuprous oxide.

In yet another embodiment of the fastener chain according to the present invention, the manner in which the hue exhibited by each of the elements changes in the length direction of the row is regular.

In yet another embodiment of the fastener chain according to the present invention, the manner in which the hue exhibited by each of the elements changes in the length direction of the row is random.

In still another embodiment of the fastener chain according to the present invention, the element is represented by the general formula: Cu _a Zn _b Ni _c (where a, b, and c are mass%, a is the balance, 5 ≦ b ≦ 40 , 0 ≦ c ≦ 30 is included, and inevitable impurities are included.) The base material is a copper alloy having a composition represented by:

In yet another embodiment of the fastener chain according to the present invention, the oxide film is an anodized film.

In another aspect, the present invention is a slide fastener including the fastener chain according to the present invention.

In yet another aspect, the present invention is an article provided with the slide fastener according to the present invention.

According to the present invention, a fastener chain having a row of copper alloy elements whose hue changes can be manufactured at low cost. Further, since the coloring step for obtaining the fastener chain according to the present invention can be carried out after the rows of elements are implanted in the fastener tape, it is easy to color the entire exposed surface of the copper alloy element. is there. In the present invention, a change in hue due to the difference in the oxidation number of copper oxide is utilized. Since copper oxide has a large change in hue due to the oxidation number, a wide range of hues can be easily created. For this reason, it is possible to use a row of elements having a large hue change or a row of elements having a small hue change according to needs. The hue can be changed regularly or randomly.

It is a figure explaining a mode that a Y-shaped member is cut | disconnected and a Y-shaped member is obtained. It is a figure explaining how to attach a fastener element to a fastener tape. It is a schematic diagram when an example of the slide fastener which concerns on this invention is seen from the front. 5 is a distribution of chromaticity a ^* and b ^* for elements according to Invention Example 1. It is distribution of chromaticity a ^* about the element which concerns on invention example 2, b ^* . It is distribution of chromaticity a ^* about the element which concerns on invention example 3, and b ^* .

An example of a slide fastener provided with a copper alloy fastener element according to the present invention will be specifically described with reference to the drawings. FIG. 3 is a schematic diagram of the slide fastener 100. As shown in FIG. 3, the slide fastener 100 includes a pair of copper alloy elements 103 that engage with each other and a row of the elements 103 on one side edge. And a pair of fastener tapes 101 attached along. A core portion 102 is formed on one end side of the fastener tape 101, and the element 103 is caulked and fixed (attached) to the core portion 102 of the fastener tape 101 at a predetermined interval. The slide fastener 100 is disposed between an upper stop 104 and a lower stop 105 that are caulked and fixed to the core portion 102 of the fastener tape 101 at the upper and lower ends of the element 103 and a pair of opposing elements 103. A slider 106 that is slidable in the vertical direction for meshing and separating is provided. A state in which the element 103 is attached to the core portion 102 of one fastener tape 101 is referred to as a slide fastener stringer, and the element 103 attached to the core portion 102 of the pair of fastener tapes 101 is engaged. What we have is called a slide fastener chain.

The base material of the element 103 is not particularly limited as long as it is a copper alloy having a composition containing copper as a main component. For example, Cu—Zn alloys such as red and brass, Cu—Zn—Ni such as white An alloy is preferable from the viewpoint of strength and workability required for the element. In particular, the general formula: Cu _a Zn _b Ni _c (where a, b, and c are mass%, a is the balance, 5 ≦ b ≦ 40, 0 ≦ c ≦ 30, and includes inevitable impurities). It is more preferable to use a copper alloy having the indicated composition as a base material because the two-phase formation due to β-phase precipitation does not occur. Inevitable impurities are present in the raw material or are inevitably mixed in the manufacturing process and are essentially unnecessary, but they are acceptable because they are very small and do not affect the characteristics. It is an impurity. In the above general formula, the content of each impurity element allowed as an inevitable impurity is generally 0.1% by mass or less, preferably 0.05% by mass or less.

In the row of the element 103 of the slide fastener, the hue exhibited by each element changes in the length direction of the row. In FIG. 3, the change in hue is schematically shown in shades. The manner of change may be regular or random.

The coloring of the element 103 may be performed on any of the slide fastener stringer, the slide fastener chain, or the slide fastener after the row of the elements 103 is fixed to the fastener tape. There is no particular limitation on the coloring method as long as the exposed surface of the element can be oxidized, but from the viewpoint of production efficiency, the electrolytic bath is moved while a long fastener stringer or fastener chain is conveyed by roll-to-roll. A method of anodizing the element in the process of passing is preferable. While passing through the electrolytic bath, the oxide film can be easily formed by bringing the anode into contact with a long fastener stringer or an element of the fastener chain for a predetermined time. In this method, since the entire element is immersed in the electrolytic bath, at least an oxide film can be formed on the entire exposed surface of the element that can come into contact with the electrolytic solution. On the other hand, it is difficult to form an oxide film on the surface where the electrolytic solution does not reach, such as the surface where the fastener tape and the element are concealed by contact.

The oxidation number of copper oxide constituting the oxide film can be changed by changing electrolytic conditions such as anode potential, current density, contact resistance (contact area between anode and element). And the hue of the element which passes an electrolytic bath can be changed regularly or irregularly by changing electrolysis conditions regularly or irregularly.

In general, when the applied voltage to the element is low, an oxide film having a high cuprous oxide (Cu ₂ O) ratio tends to be formed, and when the applied voltage to the element is high, cupric oxide ( An oxide film having a high ratio of CuO) tends to be formed. Therefore, by changing the applied voltage to the element and changing the content ratio of cuprous oxide and cupric oxide in the oxide film, brown color, dark yellow color, gunmetal color, green yellow color, copper color, Various hues such as dark blue, old gold, and lemon yellow can be created. Note that cuprous oxide itself is red, and cupric oxide itself is black.

In one embodiment of the fastener chain according to the present invention, there can be at least one element in which the content ratio of cuprous oxide in the oxide film is higher than the content ratio of cupric oxide. In one embodiment of the fastener chain according to the present invention, there can be at least one element having a cupric oxide component content in the oxide film larger than the cuprous oxide component content. In addition, in this specification, the component content rate of cuprous oxide and cupric oxide is based on molar amount.

In addition, the thickness of the oxide film increases as the oxidation time is increased, and tends to darken as the thickness of the oxide film increases. Therefore, in addition to changing the oxidation number of copper oxide, it is possible to change the hue by changing the thickness of the oxide film. The thickness of the oxide film can be, for example, about 0.05 to 1.0 μm, and typically about 0.1 to 0.5 μm.

After the anodizing treatment, the fastener stringer, slide fastener chain, or slide fastener discharged from the electrolytic bath may be washed with water and dried. It is not necessary to carry out the washing treatment many times in a bath mixed with a cleaning agent as in the case of plating treatment, and simple water washing is sufficient.

As described above, since the change in hue due to the oxidation number is large in copper oxide, the fastener chain according to the present invention can have elements having a wide range of hues. Hereinafter, a specific aspect of the hue of the element will be described using the chromaticities a ^* and b ^* as a scale.

<a ^* Ne_>
In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the largest a ^* value of the exposed surface The difference of the a ^* value with the element having the smallest a ^* value on the exposed surface can be 10 or more, 15 or more, and further 20 or more, for example 10-30 It can be a range.

In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the largest a ^* value of the exposed surface The a ^* value can be 10 or more, 15 or more, 20 or more, and further 25 or more, for example, in the range of 10-30.

In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the smallest a ^* value on the exposed surface The a ^* value can be 5 or less, can be 3 or less, can be 2 or less, for example, can be −20 to 5, and can be 0 to 5.

<B ^* value>
In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the largest b ^* value on the exposed surface The difference in b ^* value with the element having the smallest b ^* value on the exposed surface can be 20 or more, can be 25 or more, and further can be 30 or more, for example 20-50 It can be in the range or 30-40.

In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the largest b ^* value on the exposed surface The b ^* value can be 20 or more, 25 or more, 30 or more, and further 35 or more, for example, in the range of 20-40.

In one embodiment of the fastener chain according to the present invention, in the CIELAB color space defined in JIS Z8781-4 (2013), among the elements constituting the row, the element having the smallest b ^* value on the exposed surface The b ^* value can be 10 or less, can be 5 or less, can be 0 or less, can also be −5 or less, for example −20 to 10, It can be in the range of -10 to 5.

Before the formation of the oxide film, no special pretreatment is required for the exposed surface of the element. For example, degreasing treatment, pickling treatment, smoothing treatment, etc. may be performed. Accordingly, when the element uses a zinc-containing copper alloy as a base material, the surface zinc ratio is reduced by dissolving the surface zinc, and the color tone is improved.

After the formation of the oxide film, various surface treatments may be performed as necessary. For example, one or a combination of two or more surface treatments such as rust prevention treatment, clear coating treatment, waxing, matte lacquer coating, or glossy lacquer coating can be performed.

¡Slide fasteners can be attached to various items, and function especially as an opening / closing tool. The article to which the slide fastener is attached is not particularly limited, and examples thereof include daily necessaries such as clothing, bags, shoes, and miscellaneous goods, and industrial articles such as water storage tanks, fishing nets, and space suits.

Examples of the present invention will be described below, but these are provided for better understanding of the present invention and its advantages, and are not intended to limit the present invention.

(Invention Examples 1 and 2)
Cu (purity 99.99% by mass or more) and Zn (purity 99.9% by mass or more) as raw materials are melted in a melting furnace (high frequency induction heating), Cu: about 85% by mass, Zn: about 15% by mass, The balance was mixed so that the composition of the inevitable impurities was present, and a continuous wire (round wire) having a perfect cross-sectional shape was continuously cast. Next, the wire was drawn, recrystallized, and cold worked to produce a deformed wire (hereinafter referred to as “Y-bar”) having a substantially Y-shaped cross section.

Thereafter, the Y-bar is sequentially cut using a cutting die equipped with a punch and a die to obtain a large number of Y-shaped members. The convex part was press-molded to produce a fastener element. A long fastener stringer was continuously produced by caulking and fixing the leg portions of the fastener element thus produced in order along the longitudinal side edges of the fastener tape at regular intervals. And the elongate fastener chain was obtained by engaging the element row | line | column of a pair of fastener stringer.

The element rows of the obtained fastener chain were colored. Specifically, a long fastener chain was allowed to pass through the electrolytic bath while being continuously conveyed at a predetermined speed using a roll-to-roll conveyance facility. In this process, the anode was brought into contact with the fastener chain element for a predetermined time to form an oxide film. At this time, the inclination of the element when the element was in contact with the anode was changed by sandwiching the fastener chain between rollers provided with fine irregularities just before the fastener chain entered the electrolytic bath. In Invention Examples 1 and 2, the amount of inclination of the element was changed randomly. The difference between the inventive examples 1 and 2 is the magnitude of the change in the inclination of the element. The inventive example 1 has a larger change in the inclination of the element than the inventive example 2.

By changing the inclination of the element when the element contacts the anode under a constant current condition, the contact area changes and the contact resistance changes. Accordingly, the potential of the element changes accordingly, and the hue of the anodized film also changes. In this example, since the constant current condition was used, an element having a large contact resistance had a low potential and a dark blue anodic oxide film (cuprous oxide = high Cu ₂ O ratio) was obtained, and the contact resistance was small. The element became high potential and an old gold-colored anodic oxide coating (cupric oxide = CuO ratio high) was obtained. Specific coloring conditions are as follows.
<Coloring conditions>
(1) Coloring method: Anodizing method (2) Electrolytic bath composition: NaOH aqueous solution having a concentration of 30 g / L (3) Bath temperature: 50 ° C.
(4) Contact time between the anode and each element: about 15 seconds (5) Current density: 0.33 A / dm ²
The fastener chain discharged from the electrolytic bath was washed with water and then dried. The element row of the obtained fastener chain was colored on the entire exposed surface including the Y-bar cut surface, and exhibited a patch pattern in which the hue changed randomly. Further, when the thickness of the oxide film of each element was measured by cross-sectional SEM analysis, both Invention Example 1 and Invention Example 2 were in the range of 0.1 to 0.24 μm.

(Invention Example 3)
After obtaining a long fastener chain under the same conditions as in Invention Examples 1 and 2, the element rows of the fastener chain were colored. The coloring conditions were the same as those of Invention Examples 1 and 2, except that the inclination of the element when the element was in contact with the anode was regularly changed in the length direction of the element row. The element row of the obtained fastener chain was colored on the entire exposed surface including the Y-bar cut surface and exhibited a gradation color that changed regularly. Further, when the thickness of the oxide film of each element was measured by cross-sectional SEM analysis, it was in the range of 0.1 to 0.24 μm.

<Color tone test>
Each fastener chain after anodization treatment is cut out by 20 cm, and the exposed surface of all elements is 10-30 ° C. and 85% RH or less using a color difference meter CR-300 manufactured by Minolta Co., Ltd. Under the conditions, a ^* and b ^* in the CIELAB color space defined in JIS Z8781-4 (2013) were obtained. A pulsed xenon lamp was used as the light source. The results are shown in FIGS. Table 1 shows the minimum and maximum values of a ^* and b ^* in each fastener chain, and the difference between the maximum and minimum values.
<Oxide film analysis>
X-ray photoelectron spectroscopy (XPS) (X-ray photoelectron spectrometer, model: ESCALAB250Xi) manufactured by Thermo Fisher Scientific Co., Ltd. The component content of cuprous oxide and cupric oxide in the oxide film of the element was investigated, and in any example, the component content of cuprous oxide was higher than that of cupric oxide. Larger elements and elements with higher cupric oxide content content than cuprous oxide were discovered. The component content was compared based on the molar amount. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 10 Deformation line 20 Y-shaped member 21 Head 22 Engaging recessed part 23 Engaging convex part 24a, 24b Leg part 30 Element 40 Fastener tape 100 Slide fastener 101 Fastener tape 102 Core part 103 Element 104 Upper stopper 105 Lower stopper 106 Slider

Claims (12)

1. A fastener chain comprising a pair of copper alloy elements 103 that engage with each other and a pair of fastener tapes 101 that are attached to each of the rows of the elements 103 along one side edge. The fastener chain in which the hue exhibited by each of the elements 103 changes in the length direction of the row when the exposed surfaces of the layers have oxide films having different contents of cuprous oxide and cupric oxide.
2. In the CIELAB color space defined in JIS Z8771-4 (2013), among the elements 103 constituting the row, the element 103 having the largest a ^* value on the exposed surface and the element having the smallest a ^* value on the exposed surface The fastener chain according to claim 1, wherein a difference in a ^* value from 103 is 10 or more.
3. In the CIELAB color space defined in JIS Z8771-4 (2013), among the elements 103 constituting the row, the element 103 having the largest b ^* value on the exposed surface and the element having the smallest b ^* value on the exposed surface The fastener chain according to claim 1 or 2, wherein a difference in b ^* value from 103 is 20 or more.
4. JIS Z8781-4 In CIELAB color space defined by (2013), among the elements 103 constituting the column, and the largest a ^* values of the elements 103 of the a ^* value of the exposed surface 10 over the exposed surface fastener chain according to any one of claims 1 to 3 and most of the smaller element 103 a ^* value of the a ^* value is 5 or less.
5. JIS Z8781-4 In CIELAB color space defined by (2013), among the elements 103 constituting the column, is the most large b ^* values of the elements 103 of the b ^* value of the exposed surface 20 over the exposed surface fastener chain according to any one of claims 1 to 4, most of the smaller element 103 b ^* values of the b ^* value is 10 or less.
6. Among the elements 103 constituting the row, there is at least one element 103 in which the content ratio of cuprous oxide in the oxide film is larger than the content ratio of cupric oxide, and the oxide film The fastener chain according to any one of claims 1 to 5, wherein there is at least one element 103 in which a component content of cupric oxide is larger than a component content of cuprous oxide.
7. The fastener chain according to any one of claims 1 to 6, wherein a manner in which a hue exhibited by each of the elements 103 changes in a length direction of the row is regular.
8. The fastener chain according to any one of claims 1 to 6, wherein a manner in which the hue exhibited by each of the elements 103 changes in the length direction of the row is random.
9. The element 103 has a general formula: Cu _a Zn _b Ni _c (where a, b, and c are mass%, a is the balance, 5 ≦ b ≦ 40, 0 ≦ c ≦ 30, and contains unavoidable impurities. The fastener chain according to any one of claims 1 to 8, wherein the base material is a copper alloy having a composition represented by:
10. The fastener chain according to any one of claims 1 to 9, wherein the oxide film is an anodized film.
11. A slide fastener comprising the fastener chain according to any one of claims 1 to 10.
12. An article provided with the slide fastener according to claim 11.

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