Patent Publication Number: US-10760146-B2

Title: Fastening copper alloy

Description:
This application is a national stage application of PCT/JP2012/070364, which is incorporated herein by reference. 
     TECHNICAL FIELD 
     The present invention relates to a copper alloy for fastening used as fastening material. 
     BACKGROUND ART 
     Cu—Zn-based alloys are excellent in workability and have been widely used in various fields. With regard to Cu—Zn-based alloys, zinc base metal is generally more inexpensive than copper base metal. Therefore, material cost thereof can be reduced by increasing a zinc content. There exists a problem, however, that zinc element present in copper results in significant deterioration in corrosion resistance. In particular, when a copper alloy having an increased zinc content is used for a fastening material which is embedded on a base fabric through cold working, there has occurred a problem of season cracking of the material due to residual work strain. 
     Japanese Patent No. 4357869 discloses a technique in which an alloy contains elemental additives, such as Al, Si, Sn and/or Mn, and is surface-treated by means of shot-blasting or the like to be provided with compression stress in order to enhance season cracking resistance. 
     CITATION LIST 
     Patent Literature 
     
         
         [Patent Literature 1] Japanese Patent No. 4357869 
       
    
     SUMMARY OF INVENTION 
     However, the copper alloy described in Patent Literature 1 requires to be subjected to processing such as shot-blasting, thereby increasing numbers of the manufacturing processes, and this causes an increased manufacturing cost. In addition, according to Patent Literature 1, the structure of the copper alloy is made into a single phase of α in order to obtain suitable cold-workability and an increased zinc concentration in the alloy is undesirable because of causing significant formation of β-phase, which makes cold working of the alloy difficult. Therefore, in the technique described in Patent Literature 1, season cracking resistance and cold workability of the alloy have not yet been sufficiently studied when the zinc concentration in the alloy is increased to allow the α and β phases coexist. In addition, the copper alloy described in Patent Literature 1 has a problem that the zinc concentration is too low to be manufactured by extrusion. 
     In view of the problems described above, the present invention provides a copper alloy for fastening excellent in ease of manufacturing and also excellent in season cracking resistance and cold-workability. 
     According to an aspect of the present invention, in order to solve the problems described above, a copper alloy for fastening is provided, wherein the alloy has a structure of a mixture of α-phase and a β-phase; and wherein the alloy has a composition represented by the general formula: Cu bal. Zn a Mn b , where bal., a, and b are expressed in % by mass, bal. represents the balance, 34≤a≤40.5, 0.1≤b≤6, and inevitable impurities may be contained; and the composition satisfying the following equations (1) and (2):
 
 b ≥(−8 a+ 300)/7, where 34≤ a&lt; 37.5  (1),
 
 b ≤(−5.5 a+ 225.25)/5, where 35.5≤ a≤ 40.5  (2).
 
     In one embodiment, a copper alloy for fastening according to the present invention is a copper alloy for fastening wherein the alloy has a structure of a mixture of α-phase and a β-phase; and wherein the alloy has a composition represented by the general formula: Cu bal. Zn a Mn b , where bal., a, and b are expressed in % by mass, bal. represents the balance, 35≤a≤38.3, 0.2≤b≤3.5, and inevitable impurities may be contained; and the composition satisfying the following equations (3) and (4):
 
 b≥−a+ 38.5, where 35≤ a≤ 38.3  (3),
 
 b≤−a+ 40.5, where 37≤ a≤ 38.3  (4).
 
     In another embodiment of the copper alloy for fastening according to the present invention, the β-phase percentage (%) in the structure is 0.1≤β≤22 as determined from the result of observation of a cross section perpendicular to the rolled surface using an integrated peak intensity ratio in X-ray diffraction. 
     In still another embodiment of the copper alloy for fastening according to the present invention, the mean crystal grain size in the structure is 3-14 μm. 
     In yet another embodiment of the copper alloy for fastening according to the present invention, the pull-out strength after ammonia vapor test is 70% or more relative to that of Cu 85 Zn 15  material. 
     According to another aspect of the present invention, a component article for fastening formed of the above-described copper alloy for fastening is provided. 
     According to the present invention, it is possible to provide a copper alloy for fastening excellent in ease of manufacturing and also excellent in season cracking resistance and cold-workability. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a plane view showing an example of a slide fastener using a copper alloy for fastening according to an embodiment of the present invention; 
         FIG. 2  is a perspective view illustrating attachment of fastener elements and top end and bottom end stops using a copper alloy for fastening according to an embodiment of the present invention to a fastener tape; and 
         FIG. 3  is a cross sectional view showing an extrusion part of an extrusion container used to measure an extrusion surface pressure at 500° C. for a copper alloy. 
     
    
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS 
     (Copper Alloy for Fastening) 
     A copper alloy for fastening according to an embodiment of the present invention is a copper alloy of which structure consists of a mixed phase of an α-phase having a face centered cubic structure and a β-phase having a body centered cubic structure. Although season cracking sensitivity is generally known to be higher as the amount of Zn is increased, according to the intensive studies by the present inventors, it has been found that cold-workability of 80% or more can be realized and the season cracking resistance can be also enhanced by adjusting the concentrations of zinc and elemental additives in copper in suitable ranges and controlling the heating conditions and cooling conditions upon manufacturing, thereby controlling the structure such that the structure becomes a suitable α+β phase. 
     &lt;Zn&gt; 
     When the zinc content is less than 34% by mass, the consequently increased copper content leads to a higher material cost and, for a copper-zinc-manganese ternary alloy, the manganese content is increased, thereby causing a problem that the alloy cannot be a material capable of avoiding needle detection due to the increased manganese content. The term “material capable of avoiding needle detection” as used herein refers to a material corresponding to a product that can satisfy the NC-B standard (ϕ1.2 mm or less in terms of steel ball). When the zinc content exceeds 40.5%, the structure in the cast material has a β-phase percentage of 50% or more and this makes the material brittle, thereby deteriorating the cold-workability of the copper alloy and easily causing brittle fracture. The Zn content in the copper alloy is preferably 34-40.5% by mass, more preferably 35-38.3% by mass, and still more preferably 35-38% by mass. 
     &lt;Mn&gt; 
     Although Cu—Zn-based alloys have a problem that zinc element present in copper in a high concentration causes significant deterioration in corrosion resistance, addition of Mn to copper as an additional element can effectively inhibit the season cracking of the fastening materials. The addition of Mn also leads to an effect to easily make the crystal grains finer, thereby enhancing the strength. 
     It is noted that Al, Si, Sn and the like are also generally known as elemental additives which are added for the purpose of improving characteristics of copper alloys. These elemental additives, however, have large values of zinc equivalent, and thus addition thereof even in a very small amount may significantly change properties of the alloy in some cases. This makes it difficult to constantly control the quality of the copper alloy for fastening which is intended to be manufactured in mass production, thereby the ease of its manufacture cannot be improved. On the contrary, Mn has a zinc equivalent of 0.5 which is much smaller than those of other elemental additives such as Al, Si, and Sn. Therefore, comparing with other elemental additives, Mn can make a smaller quality difference of final products which may occur due to manufacturing errors, and thus provide a copper alloy for fastening excellent in quality stability and suitable for mass production. 
     With regard to the copper alloy according to the present invention, it is possible to obtain a copper alloy for fastening exhibiting both of cold-workability of 80% or more and season cracking resistance by adding Mn in an amount of 0.1% by mass or more. An excessively large Mn content results in deterioration in cold-workability. In addition, magnetization of the alloy per se may make the operation of needle detection required for the manufactured fastening material difficult. Preferably, the amount of Mn added is 0.1-6% by mass in order to prevent a high material cost due to a reduced amount of zinc, more preferably 0.1-3.5% by mass, and still more preferably 0.2-3.0% by mass in order to satisfy the NC-A standard of needle detection (0.8 mmϕ or less in terms of a steel ball). 
     &lt;Relationship Between Respective Compositions&gt; 
     Preferably, the copper alloy for fastening according to the embodiment of the present invention has a composition represented by the general formula: Cu bal. Zn a Mn b , where bal., a, and b are expressed in % by mass, bal. represents the balance, 34≤a≤40.5, 0.1≤b≤6, and inevitable impurities may be contained, and 
     the composition satisfying the following equations (1) and (2):
 
 b ≥(−8 a+ 300)/7, where 34≤ a&lt; 37.5  (1),
 
 b ≤(−5.5 a+ 225.25)/5, where 35.5≤ a≤ 40.5  (2).
 
     The reason why the relationship between respective compositions is determined as represented by equations (1) and (2) is that it is difficult to realize both of cold-workability and season cracking resistance necessary for the fastening material in the case of not satisfying equations (1) and (2). More specifically, when the concentration of Mn does not satisfy equation (1), i.e., b&lt;(−8a+300)/7, the copper alloy can be worked more easily, but may be cracked more often upon exposure to a corrosive environment such as ammonia. On the other hand, when the concentration of Mn does not satisfy equation (2), i.e., b&gt;(−5.5a+225.25)/5, the structure becomes brittle and cold-workability is deteriorated though less cracking occurs. 
     More preferably, the copper alloy for fastening according to the embodiment of the present invention is a copper alloy further satisfying equations (3) and (4) below:
 
 b≥−a+ 38.5, where 35≤ a≤ 38.3  (3),
 
 b≤−a+ 40.5, where 37≤ a≤ 38.3  (4).
 
     When the copper alloy has a composition satisfying equations (3) and (4), the color tone in appearance of the finally obtained copper alloy very closely approaches to that of existing Cu 85 Zn 15  alloy which the customers desire. Therefore, even when fastening materials are manufactured in mass production using the copper alloy according to the present invention, color tone changes to a lesser degree among the fastening materials. Further, the β-phase is easily controlled to a desired ratio, thereby successfully providing fastening materials at a high yield and excellent in quality stability and appearance. In addition, the copper alloy is a more useful material as a fastening material capable of avoiding needle detection. 
     &lt;Percentage of α-Phase and β-Phase&gt; 
     Control of the percentage of α-phase and β-phase in the copper alloy is important in order to improve season cracking resistance and cold-workability required for the fastening materials. Control of the percentage of α-phase and β-phase can be attained by adjusting the heating conditions and subsequent cooling conditions. 
     According to the copper alloy according to the embodiment of the present invention, preferably the β-phase percentage (%) in the crystalline structure is 0.1≤β≤22, and more preferably 0.5≤β≤20.5. The reason for that is when the β-phase percentage is excessively high, the cold-workability cannot be ensured and when the β-phase percentage is excessively low, sufficient season cracking resistance cannot be obtained in spite of containing manganese. It is noted that the “β-phase percentage in the crystalline structure” refers to a value as calculated by:
 
β-Phase percentage (%)=(Integrated β-phase peak intensity value)/(Integrated α-phase peak intensity value+Integrated β-phase peak intensity value)×100,
 
where the integrated peak intensity values of the α-phase and the β-phase are calculated by performing polishing with SiC water-proof polishing paper and performing mirror-finishing with diamond to expose a cross section perpendicular to the rolled surface, and analyzing the cross section by X-ray diffraction (θ−2θ method).
 
&lt;Crystal Grain Size&gt;
 
     With regard to the copper alloy according to the embodiment of the present invention, preferably the mean crystal grain size in the structure is 14 μm or less, and, for example, 3-13.5 μm. The mean crystal grain size is not particularly limited for the lowest value, but is preferably 0.1 μm or more in order for homogeneous recrystallization. In the present embodiment, the term “mean crystal grain size” refers to a value of length of the mean crystal grain size determined by drawing 20 lines at random or arbitrarily on an metal structure observation photograph obtained by observation using an electron microscope or an optical microscope from the edge to edge of the observation photograph, measuring the length of these lines and correcting the length by comparing with the actual scale, and dividing the corrected length of the lines by a number of the grain boundaries crossing the lines. That is, the mean crystal grain size is evaluated by: (Mean crystal grain size)=(Total length of the lines drawn on the photograph corrected to the actual length (length of 20 lines)/(number of grain boundaries crossing the lines drawn on the photograph). 
     &lt;Properties&gt; 
     The copper alloy for fastening according to the embodiment of the present invention can exhibit a pull-out strength after ammonia vapor test of 70% or more relative to that of Cu 85 Zn 15  material, and for this alloy, the cold-workability can be 80% or more, and the extrusion surface pressure at 500° C. can be 1100 MPa or less, which corresponds to 65% or less as a percentage to that of Cu 85 Zn 15  material. It is meant by this value of the extrusion surface pressure at 500° C. that the lifetime of the die can be prolonged because the yield strength at 500° C. of a typical steel material for the die is approximately 1400 MPa. In addition, the copper alloy for fastening according to the embodiment of the present invention is not only effective in cold working processes but also is sufficiently usable in hot working processes. Accordingly, it is possible to provide a material from which even a fastener of No. 5 size (a size in which the element width is 5.5 mm or more and less than 7.0 mm in a state where a pair of the fastener elements engage with each other) with high strength can be manufactured, of which season cracking resistance and stress corrosion resistance can be improved, and which is easily worked and suitable for mass production. It is noted that the details of the evaluation methods for ammonia vapor test, the cold-workability and the extrusion surface pressure at 500° C. will be described in Examples below. 
     &lt;Component Articles for Fastening&gt; 
     Examples of component articles for fastening suitable for the copper alloy for fastening according to the present invention are described, referring to the drawings. It is noted although the description takes parts composing a slide fastener as examples for the component articles for fastening in the following embodiment, the present invention can be similarly applied for products formed of a copper alloy other than the fastening materials described below or intermediate products prior to obtaining the final products (e.g., long wire rods described below). 
     Though the copper alloy for fastening according to the present invention can be utilized for component articles for fastening, such as a fastener element, an top end stop, a bottom end stop, a retaining box and a slider, the copper alloy can be also utilized for a variety of fastening materials other than the parts exemplified herein, as a matter of course. Here, explanations are made, taking an example of a slide fastener  1 . 
     The slide fastener  1  includes, for example as shown in  FIG. 1 , a pair of right and left fastener stringers  2  on which element rows  4  are formed by attaching a plurality of fastener elements  10  in rows on the side edges of fastener tapes  3  opposing to each other, top end stops  5  and bottom end stop  6  attached at the top end parts and the bottom end parts of the right and left fastener stringers  2  along with the element rows  4 , respectively, and a slider  7  slidably arranged along with the element rows  4 . 
     Each fastener element  10  is manufactured by, as shown in  FIG. 2 , slicing a wire rod  20  having a generally Y-shaped cross section, referred to as Y-bar, at a predetermined thickness, and subjecting the sliced element material  21  to press working or the like to form an engaging head  10   a.    
     The fastener element  10  includes the engaging head  10   a  formed by press working or the like, a body part  10   b  extended in one direction from the engaging head  10   a , and a pair of leg parts  10   c  bifurcated and extended from the body part  10   b . The fastener elements  10  are attached to the fastener tape  3  at predetermined intervals by caulking the leg parts  10   c  in a direction in which both of the leg parts  10   c  approach to each other (inward) to plastically deform the leg parts  10   c  in a state where the element-attaching part of the fastener tape  3  including a core string part  3   a  has been inserted between a pair of the leg parts  10   c.    
     The top end stop  5  for the slide fastener  1  is manufactured by slicing a flat rectangle  5   a  having a rectangular-shaped cross section at a predetermined thickness and bending the obtained cut piece to form an article having a generally U-shaped cross section. In addition, the top end stop  5  is attached to each of the right and left fastener tapes  3  by caulking the top end stop  5  to plastically deform the top end stop  5  in a state where the element-attaching part of the fastener tape  3  has been inserted into the space at the inner surface side of the top end stop  5 . 
     The bottom end stop  6  for the slide fastener  1  is manufactured by slicing a deformed wire rod  6   a  having a generally H-shaped (or generally X-shaped) cross section at a predetermined thickness. In addition, the bottom end stop  6  is attached to the right and left fastener tapes  3  straddling the both tapes by caulking the bottom end stop  6  to plastically deform the bottom end stop  6  in a state where the element-attaching parts of the right and left fastener tapes  3  have been inserted into the spaces at the inner surface side of the right and left parts of the bottom end stop  6 , respectively. 
     The fastening materials, such as fastener element  10 , the top end stop  5 , the bottom end stop  6  and the slider  7 , are often subjected to cold-working and have tensile residual stress caused by this cold-working, and therefore season cracking has often happened for the alloys containing a large amount of zinc. According to the copper alloy according to the embodiment of the present invention, the alloy can be that can realize cold-workability of 80% or more and is excellent in season cracking resistance by adjusting the concentrations of zinc and the elemental additives in copper in suitable ranges and controlling the heating conditions and cooling conditions upon manufacturing, thereby controlling the structure such that the structure becomes a suitable α+β phase. 
     &lt;Manufacturing Method&gt; 
     Examples of methods for manufacturing a component article for fastening using the copper alloy for fastening are described. 
     When the fastener element  10  shown in  FIG. 1  is manufactured, first a copper-zinc alloy casting material having a predetermined cross-sectional area is manufactured. Upon casting, the casting material is cast, while adjusting the copper-zinc alloy composition such that the zinc content is preferably 34-40.5% by mass, more preferably 35-38.3% by mass, and still more preferably 35-38% by mass. 
     Subsequently, after manufacturing the casting material, the percentage of the α-phase and the β-phase in the copper-zinc alloy is controlled such that the β-phase percentage is 0.1≤β≤22, more preferably 0.5≤β≤20.5 by subjecting the casting material to cold wire drawing into a wire rod having a desired wire diameter and to heat treatment. The conditions of the heat treatment to which the casting material is subjected can be arbitrarily set depending on the composition of the copper-zinc alloy. 
     After controlling the β-phase percentage in the casting material, a long wire rod, which is an intermediate product, is manufactured by subjecting the cast material to cold working such as cold extrusion such that the working reduction percentage is, for example, 80% or more. The cold working is carried out at a temperature below the recrystallization temperature of the copper-zinc alloy, and it is preferred to carry out the cold working at a temperature of 200° C. or below, and particularly at a temperature of 100° C. or below. 
     Subsequently, the above-described Y-bar  20  is formed by passing the cold-worked long wire rod through a plurality of rolling rolls to perform cold working such that the cross section of the wire rod becomes a generally Y-shape. The fastener element  10  according to the present embodiment can be manufactured by slicing Y-bar  20  at a predetermined thickness and subjecting the sliced element material  21  to press work using a forming punch and a forming die or the like to form the engaging head  10   a . It is noted that deformed wire rods such as the Y-bar can be also directly manufactured by directly extruding the casting material at 400° C. or above since the copper alloy according to the present invention is also excellent in hot-extrudability. 
     In the case of the top end stop  5 , first a casting material made of a copper-zinc alloy having the similar composition to that of the fastener element  10  is cast, and then the casting material is subjected to heat treatment to control the β-phase percentage in the copper-zinc alloy. Subsequently, the obtained casting material is subjected to cold working to manufacture a flat rectangle  5   a  (intermediate product) having a rectangular-shaped cross section. Then the top end stop  5  can be manufactured by slicing the obtained flat rectangle  5   a  at a predetermined thickness as shown in  FIG. 2  and bending the obtained cut piece to form an article having a generally U-shaped cross section. 
     In the case of the bottom end stop  6 , first a casting material made of a copper-zinc alloy having a similar composition to that of the fastener element  10  and the top end stop  5  is cast, and then the casting material is subjected to heat treatment to control the β-phase percentage in the copper-zinc alloy. Subsequently, the obtained casting material is subjected to cold working to manufacture a deformed wire rod  6   a  (intermediate product) having a generally H-shaped (or generally X-shaped) cross section. Then the bottom end stop  6  can be manufactured by slicing the obtained deformed wire rod  6   a  at a predetermined thickness as shown in  FIG. 2 . 
     EXAMPLES 
     Hereinafter, Examples together with Comparative Examples of the present invention will be presented and these Examples are provided in order for a better understanding of the present invention and advantages thereof, and it is not intended that the present invention is limited to the Examples. 
     Copper, zinc, and various elemental additives were weighed so as to make the alloy compositions as shown in Table 1 below, these ingredients were melted under an argon atmosphere using a high frequency vacuum melting apparatus to manufacture an ingot having a diameter of 40 mm, and then an extruded material having a diameter of 8 mm was manufactured from the obtained ingot. The obtained extruded material was subjected to cold working until the material became a predetermined plate having a plate thickness ranging 4.0-4.2 mm. 
     The plate material was subjected to heat treatment at a temperature in the range of 400° C. or above to 700° C. or below and then the heat-treated plate material was annealed. The plate material in which work strain was removed by the heat treatment was subjected to cold rolling where the plate material was rolled only from the vertical directions to manufacture a long plate material having a thickness of 1 mm or less. Test pieces with a plate thickness of 0.8 mm, a plate width of 10 mm, and a plate length of predetermined value (length in the rolling direction) were cut from the resulting plate material. 
     &lt;Evaluation of β Percentage&gt; 
     For each resulting test piece, the structure of the copper-zinc alloy on a cross section perpendicular to the rolled surface was observed with a cross sectional photograph. The cross section perpendicular to the rolled surface was exposed by polishing with SiC water-proof polishing paper (#180-#2000), was further mirror-finished with diamond paste 3 μm, 1 μm, and then X-ray diffraction measurement was carried out using the polished cross section as a test piece. GADDS-Discover 8 (Bruker AXS K.K.) was used as a measuring apparatus for a measuring time of 90 sec. for the lower angle side and 120 sec. for the higher angle side and the integrated peak intensity ratios of the α-phase and β-phase were calculated, respectively. The β-phase percentage was calculated as follows:
 
β-phase percentage (%)=(Integrated β-phase peak intensity value)/(Integrated α-phase peak intensity value+Integrated β-phase peak intensity value)×100.
 
&lt;Evaluation of Cold Workability&gt;
 
     The plate material having a plate thickness of 4.0-4.2 mm obtained by the above-described process was subjected to air annealing at 500° C. for 6 hours, and then the plate-like test pieces were subjected to milling in order to remove an oxide film formed on the surface, and to finishing the surface with SiC water-proof polishing paper (#800) to manufacture the test pieces for cold workability evaluation. The finished dimensions of the test piece for cold-workability evaluation were a plate thickness of 3.5 mm, a plate width of 7.5 mm, and a plate length of a predetermined value. The draft limit based on the following equation was evaluated using a rolling mill. The draft limit was defined as a draft at the pass just before the pass where cracking occurred on the material.
 
(Draft) (%)=[(Plate thickness at start of rolling−Plate thickness after rolling)/(Plate thickness at start of rolling)]×100
 
&lt;Extrusion Pressure at 500° C.&gt;
 
     Copper, zinc, and various elemental additives were weighed so as to make the alloy compositions as shown in Table 1, these ingredients were melted under an argon atmosphere using a high frequency vacuum melting apparatus to manufacture an ingot (a billet) having a diameter of 40 mm. An extruder container  31  shown in  FIG. 3  was set at 500° C. and the billet  32  was heated in an atmospheric furnace set at 800° C. for 30 minutes, and then the billet  32  was inserted into the extruder container (inner diameter 42 mmϕ). A stem  33  was arranged on the billet  32 , the billet  32  was pressed by the stem  33  to be extruded through a die  34  for a 8 mmϕ material arranged on the front face of the extruder container  31 , the maximum load during the extrusion was measured, the maximum surface pressure was calculated from the maximum load, and “Extrusion surface pressure at 500° C.” was defined as this maximum surface pressure. 
     &lt;Evaluation of Mean Pull-Out Strength after Exposure to Ammonia&gt; 
     The exposure test to ammonia was carried out according to Japan Copper and Brass Association Technical Standard JBMA-T301, Ammonia test method of copper alloy wrought material (JBMA method). It is noted that fastener chains of No. 5 were exposed to ammonia atmosphere, washed and then used as test pieces for evaluation of the fastener product. The resulting elements of the fastener chains as the test pieces were stretched by a tensile testing machine, and the obtained mean value of the load was defined as the mean pull-out strength. The results are shown in Table 1. It is noted that, in Table 1, “Excellent” refers to the case where the mean pull-out strength is 85% or more, “Good” refers to the case where the mean pull-out strength is 70% or more and less than 85%, “Fair” refers to the case where the mean pull-out strength is 55% or more and less than 70%, and “Poor” refers to the case where the mean pull-out strength is less than 55%, based on the pull-out strength for Cu 85 Zn 15  material (Comparative Example 1). 
     &lt;Needle Detection Standard&gt; 
     Needle detection performance was evaluated using the test pieces used in &lt;Evaluation of mean pull-out strength after exposure to ammonia&gt; described above. The case where the needle detection value of the test piece was 0.8 mmϕ or less in terms of a steel ball was evaluated as NC-A standard, and the case where the needle detection value was 1.2 mmϕ or less in terms of a steel ball was evaluated as NC-B standard. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                   
                   
                   
                 Extrusion 
                 Mean pull-out 
                 Mean crystal 
                   
               
               
                   
                   
                 β Per- 
                   
                 pressure 
                 strength after 
                 grain size of 
                 Needle 
               
               
                   
                 Alloy composition (wt %) 
                 centage 
                 Cold 
                 at 500° C. 
                 exposure to 
                 evaluated 
                 detection 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Cu 
                 Zn 
                 Mn 
                 Al 
                 Si 
                 Sn 
                 (%) 
                 workability 
                 (MPa) 
                 ammonia 
                 material (μm) 
                 standard 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Example 1 
                 60.2 
                 37.6 
                 2.2 
                 0 
                 0 
                 0 
                 14 
                 Pass at 80% 
                 935 
                 Good 
                 3.7 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 2 
                 59.6 
                 34.8 
                 5.6 
                 0 
                 0 
                 0 
                 13 
                 Pass at 80% 
                 854 
                 Good 
                 3.9 
                 NC-B 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 3 
                 61 
                 38.1 
                 0.9 
                 0 
                 0 
                 0 
                 5.6 
                 Pass at 80% 
                 995 
                 Excellent 
                 10.8 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 4 
                 59.9 
                 39.2 
                 0.9 
                 0 
                 0 
                 0 
                 17.5 
                 Pass at 80% 
                 898 
                 Excellent 
                 8.7 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 5 
                 61 
                 38.6 
                 0.4 
                 0 
                 0 
                 0 
                 7.2 
                 Pass at 80% 
                 963 
                 Excellent 
                 12.8 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 6 
                 60 
                 39.6 
                 0.4 
                 0 
                 0 
                 0 
                 19.3 
                 Pass at 80% 
                 882 
                 Excellent 
                 8.2 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 7 
                 59.8 
                 40 
                 0.2 
                 0 
                 0 
                 0 
                 20.4 
                 Pass at 80% 
                 910 
                 Excellent 
                 7.7 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 8 
                 61.4 
                 35.8 
                 2.8 
                 0 
                 0 
                 0 
                 0.8 
                 Pass at 80% 
                 1053 
                 Good 
                 13.2 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Example 9 
                 60.4 
                 35.8 
                 3.8 
                 0 
                 0 
                 0 
                 7 
                 Pass at 80% 
                 1016 
                 Good 
                 10.5 
                 NC-A 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 85 
                 15 
                 0 
                 0 
                 0 
                 0 
                 0 
                 Pass at 80% 
                 1800 or more 
                 Excellent 
                 n.d. 
                 NC-A 
               
               
                 Example 1 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 65 
                 35 
                 0 
                 0 
                 0 
                 0 
                 0 
                 Pass at 80% 
                 1191 
                 Poor 
                 15.7 
                 NC-A 
               
               
                 Example 2 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 60.6 
                 39.4 
                 0 
                 0 
                 0 
                 0 
                 14 
                 Pass at 80% 
                 924 
                 Poor 
                 7.9 
                 NC-A 
               
               
                 Example 3 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 59.5 
                 40.5 
                 0 
                 0 
                 0 
                 0 
                 23 
                 Pass at 80% 
                 877 
                 Fair 
                 9.0 
                 NC-A 
               
               
                 Example 4 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 59.2 
                 40.8 
                 0 
                 0 
                 0 
                 0 
                 29 
                 Pass at 80% 
                 812 
                 Fair 
                 11.3 
                 NC-A 
               
               
                 Example 5 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 60.6 
                 39.4 
                 0 
                 0 
                 0 
                 0 
                 39 
                 Pass at 80% 
                 924 
                 Fair 
                 7.4 
                 NC-A 
               
               
                 Example 6 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 61.2 
                 38.8 
                 0 
                 0 
                 0 
                 0 
                 40 
                 39% 
                 1063 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 7 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 58 
                 42 
                 0 
                 0 
                 0 
                 0 
                 45 
                 39% 
                 689 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 8 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 65.5 
                 34 
                 0.5 
                 0 
                 0 
                 0 
                 0 
                 Pass at 80% 
                 1250 
                 Poor 
                 14.2 
                 NC-A 
               
               
                 Example 9 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 63.6 
                 34.3 
                 2.1 
                 0 
                 0 
                 0 
                 0 
                 Pass at 80% 
                 1150 
                 Poor 
                 12.3 
                 NC-A 
               
               
                 Example 10 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 61.2 
                 38.8 
                 0 
                 0 
                 0 
                 0 
                 18.8 
                 Pass at 80% 
                 1063 
                 Poor 
                 9.6 
                 NC-A 
               
               
                 Example 11 
                   
                   
                   
                   
                   
                   
                   
                 or more 
               
               
                 Comparative 
                 65.8 
                 34.2 
                 0 
                 1.2 
                 0 
                 0 
                 21.1 
                 71% 
                 878 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 12 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 66.2 
                 33.8 
                 0 
                 2.9 
                 0 
                 0 
                 100 
                 10% 
                 774 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 13 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.9 
                 39.1 
                 0 
                 0.5 
                 0 
                 0 
                 49 
                 63% 
                 683 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 14 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 59.9 
                 38.6 
                 0 
                 1.5 
                 0 
                 0 
                 100 
                 20% 
                 640 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 15 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 59 
                 38.1 
                 0 
                 2.9 
                 0 
                 0 
                 100 
                 20% 
                 829 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 16 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.3 
                 35.8 
                 0 
                 3.9 
                 0 
                 0 
                 100 
                 20% 
                 845 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 17 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 64.1 
                 34.4 
                 0 
                 0 
                 1.5 
                 0 
                 38 
                 39% 
                 878 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 18 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 62.7 
                 34.3 
                 0 
                 0 
                 3 
                 0 
                 86 
                 10% 
                 774 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 19 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.5 
                 39.2 
                 0 
                 0 
                 0.3 
                 0 
                 40.1 
                 39% 
                 738 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 20 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.2 
                 39.3 
                 0 
                 0 
                 0.5 
                 0 
                 51.2 
                 39% 
                 731 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 21 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.3 
                 39.3 
                 0 
                 0 
                 0.4 
                 0 
                 55.4 
                 22% 
                 700 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 22 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.3 
                 39 
                 0 
                 0 
                 0.7 
                 0 
                 79.6 
                 20% 
                 685 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 23 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 64.8 
                 34.2 
                 0 
                 0 
                 0 
                 1.0 
                 18 
                 71% 
                 1016 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 24 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 64.3 
                 33.7 
                 0 
                 0 
                 0 
                 2.0 
                 12 
                 35% 
                 925 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 25 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.4 
                 38.6 
                 0 
                 0 
                 0 
                 1.0 
                 44.8 
                 63% 
                 783 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 26 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 59.7 
                 38.3 
                 0 
                 0 
                 0 
                 2.0 
                 43.4 
                 27% 
                 726 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 27 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 59 
                 37.9 
                 0 
                 0 
                 0 
                 3.1 
                 45.1 
                 10% or less 
                 656 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 28 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                 Comparative 
                 60.4 
                 37.5 
                 2.1 
                 0 
                 0 
                 0.0 
                 40.5 
                 71% 
                 924 
                 Poor 
                 Not 
                 Not 
               
               
                 Example 29 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 evaluable 
                 evaluable 
               
               
                   
               
            
           
         
       
     
     All of Examples 1-9 exhibited excellent cold-workability of 80% or more and extrusion surface pressure of 850-1100 N at 500° C. Pull-out strengths after ammonia vapor test for all of Examples 1-9 are also “excellent” or “Good,” and these results show that copper alloys excellent in season cracking resistance and cold workability were obtained. 
     Comparative Example 1 is excellent in cold-workability and season cracking resistance but has a low zinc concentration, thereby increasing the material cost. In addition, Comparative Example 1 exhibited a high extrusion surface pressure at 500° C., and therefore production using extrusion is difficult. 
     All of Comparative Examples 2-6 and 11, which are examples added with no Mn as an additional element, exhibited low pull-out strength after ammonia vapor test, thereby being inferior in season cracking resistance. 
     Comparative Examples 7 and 8 exhibited a draft limit of only about 39% and are inferior in cold workability due to the β-phase percentage as high as 40%. In addition, both of Comparative Examples 7 and 8 did not exhibit high cold-workability comparable to that for Examples 1-9 but exhibited too low cold-workability to make the test pieces for ammonia vapor test, and the test pieces could not be made in a state of having residual stress after cold working, thereby failing in evaluation of the crystal grain size. 
     Both of Comparative Examples 9 and 10 do not have structure of the mixed phase of α+β phase and also are inferior in season cracking resistance in spite of addition of Mn as an additional element. 
     Comparative Examples 12-17 show examples added with Al as an additional element. All of Comparative Examples 12-17 did not exhibit high cold-workability comparable to that for Examples 1-9 but exhibited too low cold-workability to make the test pieces for ammonia vapor test, and the test pieces could not be made in a state of having residual stress after cold working. 
     Comparative Examples 18-23 are examples added with Si as an additional element and Comparative Examples 24-28 are examples added with Sn as an additional element. All of Comparative Examples 18-28 did not exhibit high cold-workability comparable to that for Examples 1-9 but exhibited too low cold-workability to make the test pieces for ammonia vapor test. Comparative Example 29 is an example which has a composition within the composition range of the present invention and a higher β-phase percentage. Similarly to the above, Comparative Example 29 did not exhibit high cold-workability comparable to Examples but exhibited too low cold-workability to make the test pieces for ammonia vapor test. 
     DESCRIPTION OF REFERENCE NUMBERS 
     
         
           1  Slide fastener 
           2  Fastener stringer 
           3  Fastener tape 
           4  Element row 
           5  Top end stop 
           5   a  Flat rectangle 
           6  Bottom end stop 
           6   a  Deformed wire rod 
           7  Slider 
           10  Fastener element 
           10   a  Engaging head 
           10   b  Body part 
           10   c  Leg part 
           10   c  Leg parts 
           20  Y-bar (wire rod) 
           21  Element material 
           31  Extruder container 
           32  Billet 
           33  Stem 
           34  Die