Copper alloy wire, copper alloy twisted wire, coated electric wire, and electric wire having terminal

Abstract

Provided is a copper alloy wire having: a composition comprising a copper alloy containing 0.05-1.60 mass % of iron, 0.01-0.70 mass % of phosphorus, and 0.05-0.70 mass % of tin; a wire diameter of 0.1-15.0 mm; and a cross section that has a central part and an outer peripheral part, wherein the GROD value of the central part measured by electron backscatter diffraction is 23° or less.

Description

Copper alloy wires, copper alloy stranded wires, insulated wires, and wires with terminals 【0001】 This disclosure relates to copper alloy wires, copper alloy stranded wires, insulated wires, and wires with terminals. 【0002】 Patent Document 1 discloses a copper alloy wire made of a copper alloy containing specific additive elements in predetermined proportions. The specific additive element is at least one selected from the group consisting of iron (Fe), titanium (Ti), tin (Sn), silver (Ag), magnesium (Mg), zinc (Zn), chromium (Cr), and phosphorus (P). This copper alloy wire is manufactured by drawing a cast wire made by continuous casting. Hereinafter, the copper alloy wire will simply be referred to as copper alloy wire. 【0003】 Japanese Patent Publication No. 2015-203136 【0004】 The copper alloy wire of this disclosure comprises a composition consisting of a copper alloy containing 0.05% to 1.60% by mass of iron, 0.01% to 0.70% by mass of phosphorus, and 0.05% to 0.70% by mass of tin, a wire diameter of 0.1 mm to 15.0 mm, and a cross-section having a central part and an outer periphery. The GROD value of the central part, measured by electron beam backscatter diffraction, is 23° or less. 【0005】 Figure 1 is a schematic diagram showing an example of a copper alloy wire according to the embodiment. Figure 2 is a cross-sectional view taken along line II-II of Figure 1. Figure 3 is a schematic diagram illustrating the casting structure angle of the cast wire during the manufacturing process of the copper alloy wire according to the embodiment. Figure 4 is a schematic perspective view showing a coated electric wire according to the embodiment. Figure 5 is a schematic side view showing the vicinity of the terminal portion of an electric wire with a terminal according to the embodiment. 【0006】 [Problems this disclosure aims to solve] Cast wire rods made of copper alloys may have a structure in which additive elements are segregated at grain boundaries, or a structure in which compounds containing additive elements are unevenly distributed. When cast wire rods having the above structure are subjected to wire drawing, breakage due to the above structure is likely to occur. Copper alloy wires obtained by drawing cast wire rods that are prone to breakage tend to have inferior mechanical properties. 【0007】 One of the objectives of this disclosure is to provide a copper alloy wire with excellent mechanical properties. 【0008】 [Effects of this disclosure] The copper alloy wire of this disclosure has excellent mechanical properties. 【0009】 [Description of Embodiments of the Disclosure] First, embodiments of the Disclosure will be listed and described. 【0010】 (1) The copper alloy wire according to the embodiment of the present disclosure comprises a composition consisting of a copper alloy containing 0.05% by mass or more and 1.60% by mass or less iron, 0.01% by mass or more and 0.70% by mass or less phosphorus, and 0.05% by mass or more and 0.70% by mass or less tin, a wire diameter of 0.1 mm or more and 15.0 mm or less, and a cross-section having a central part and an outer part. The GROD value of the central part measured by electron beam backscatter diffraction is 23° or less. 【0011】 The GROD (Grain Reference Orientation Deviation) value is obtained by electron backscatter diffraction and indicates the difference in orientation from a reference orientation within a single crystal grain. By observing this crystal orientation difference, it is possible to infer the residual strain within the crystal grain. 【0012】 Copper alloy wires made from copper alloys containing iron, phosphorus, and tin as additive elements within the above ranges exhibit excellent tensile strength. In particular, copper alloy wires with a central GROD value of 23° or less have excellent mechanical properties throughout their entire length because the central part is not brittle. Copper alloy wires with a central GROD value of 23° or less are less prone to breakage during the manufacturing process and offer excellent productivity. Copper alloy wires with a central GROD value of 23° or less are manufactured by drawing cast wire rods with a central GROD value of 23° or less. When the GROD value exceeds 23°, the residual strain is large, and the areas where this residual strain accumulates become brittle. When cast wire rods with a GROD value exceeding 23° are drawn, breakage is likely to occur starting from the areas where residual strain has accumulated. In other words, cast wire with a central GROD value of 23° or less is less prone to breakage, and copper alloy wire obtained by drawing this break-resistant cast wire is not only highly productive but also possesses excellent mechanical properties. 【0013】(2) In the copper alloy wire described in (1) above, the central part may be the interior of a circle with a radius of 1 / 8 of the wire diameter, with the central axis of the copper alloy wire as the center. 【0014】 Copper alloy wires with a GROD value of 23° or less in a relatively narrow central area tend to have high mechanical properties along their entire length. 【0015】 (3) In the copper alloy wire described in (1) or (2) above, the outer periphery is a region other than the central part, and the GROD value of the outer periphery measured by electron beam backscatter diffraction may be 23° or less. 【0016】 Copper alloy wires with a GROD value of 23° or less in both the core and outer circumference are less prone to embrittlement in the core, and tend to have high mechanical properties along their entire length. 【0017】 (4) In any of the copper alloy wires described in (1) to (3) above, the outer surface of the copper alloy wire may have processing marks. 【0018】 The presence of processing marks on the outer surface of the copper alloy wire indicates that it is a copper alloy wire obtained by applying a corresponding processing to a cast wire. The processing marks are, for example, wire drawing marks. As mentioned above, copper alloy wire with a central GROD value of 23° or less is manufactured by drawing a cast wire with a central GROD value of 23° or less. Copper alloy wire obtained by drawing a cast wire with a central GROD value of 23° or less has excellent productivity and excellent mechanical properties. 【0019】 (5) In any of the copper alloy wires described in (1) to (4) above, the tensile strength may be 250 MPa or more. 【0020】 Copper alloy wires with a tensile strength of 250 MPa or more have excellent strength. 【0021】 (6) The copper alloy stranded wire according to the embodiment of the present disclosure is made by twisting together a plurality of copper alloy wires according to any of (1) to (5) above. 【0022】Stranded wire exhibits superior flexibility compared to single wire with the same cross-sectional area, and each strand is less likely to break even when subjected to impact and repeated bending. Therefore, the above-mentioned copper alloy stranded wire has excellent impact resistance and fatigue properties. 【0023】 (7) An insulated wire according to an embodiment of the present disclosure comprises a conductor and an insulating layer covering the outer circumference of the conductor, wherein the conductor comprises the copper alloy stranded wire described in (6) above. 【0024】 The above-mentioned insulated wire has a conductor made of copper alloy stranded wire, which has excellent impact resistance and fatigue characteristics, and therefore has excellent impact resistance and fatigue characteristics. 【0025】 (8) The wire with a terminal according to the embodiment of the present disclosure comprises the insulated wire described in (7) above and a terminal portion attached to the end of the insulated wire. 【0026】 The above-mentioned wire with terminals is composed of a coated wire that has excellent impact resistance and fatigue characteristics, and therefore has excellent impact resistance and fatigue characteristics. 【0027】 [Details of Embodiments of the Disclosure] Specific examples of copper alloy wires, copper alloy stranded wires, insulated wires, and terminal wires of the Disclosure will be described with reference to the drawings. Identical reference numerals in the drawings indicate the same or corresponding parts. In each drawing, some parts of the configuration may be exaggerated or simplified for illustrative purposes. The dimensional ratios of parts in the drawings may also differ from those of the actual components. The present invention is not limited to these examples, but is indicated by the claims, and all modifications within the meaning and scope of the claims are intended to be included. 【0028】 <Copper Alloy Wire> <Overview> The copper alloy wire 1 of this embodiment has a composition consisting of a copper alloy containing specific additive elements in predetermined proportions, a wire diameter 1d as shown in Figure 1, and a cross-section 2 as shown in Figure 2. The cross-section 2 comprises a central part 3 and an outer peripheral part 4. One of the features of the copper alloy wire 1 of this embodiment is that the GROD value of the central part 3, measured by electron beam backscatter diffraction, is 23° or less. The copper alloy wire 1 is manufactured by drawing a cast wire. 【0029】<<Composition>> The composition of the copper alloy wire 1 contains additive elements, and the balance is a copper alloy composed of copper (Cu) and inevitable impurities. The copper alloy is an alloy that contains the most copper. The additive elements include iron (Fe), phosphorus (P), and tin (Sn) as essential additive elements. The content ratio of iron is 0.05% by mass or more and 1.60% by mass or less. The content ratio of phosphorus is 0.01% by mass or more and 0.70% by mass or less. The content ratio of tin is 0.05% by mass or more and 0.70% by mass or less. The copper alloy wire 1 made of a copper alloy containing iron, phosphorus, and tin within the above ranges is excellent in tensile strength. The content ratio of each element in the composition is the mass ratio of each element when the composition of the copper alloy is 100% by mass. 【0030】 The content ratio of iron may be 0.10% by mass or more and 1.50% by mass or less, or 0.20% by mass or more and 1.40% by mass or less. The content ratio of phosphorus may be 0.03% by mass or more and 0.60% by mass or less, or 0.05% by mass or more and 0.50% by mass or less. The content ratio of tin may be 0.07% by mass or more and 0.60% by mass or less, or 0.10% by mass or more and 0.50% by mass or less. 【0031】 The composition of the copper alloy wire 1 may contain additive elements other than iron, phosphorus, and tin, or may not contain them. Any additive elements other than iron, phosphorus, and tin are, for example, silver (Ag), magnesium (Mg), nickel (Ni), and silicon (Si). Any additive elements other than iron, phosphorus, and tin may be one kind or two or more kinds. That is, the composition of the copper alloy wire 1 may contain at least one kind of essential additive element and any additive element, and the balance may be composed of inevitable impurities and copper. 【0032】 The total content ratio of the additive elements including both the essential additive elements and the optional additive elements is, for example, 0.11% by mass or more and 3.10% by mass or less, 0.12% by mass or more and 3.00% by mass or less, or 0.13% by mass or more and 2.90% by mass or less. 【0033】≪Wire Diameter≫ The wire diameter 1d of copper alloy wire 1 is 0.1 mm or more and 15.0 mm or less. If the wire diameter 1d is 0.1 mm or more, the degree of wire drawing in the manufacturing process of copper alloy wire 1 can be increased. A greater degree of wire drawing tends to increase the strength of the copper alloy wire 1 produced by work hardening. If the wire diameter 1d is 15.0 mm or less, the casting speed in the manufacturing process of copper alloy wire 1 can be increased. A faster casting speed allows for more productive production of copper alloy wire 1. The casting speed will be discussed later. The wire diameter 1d of copper alloy wire 1 may also be 0.11 mm or more and 14.0 mm or less, or 0.12 mm or more and 13.0 mm or less. The wire diameter 1d of copper alloy wire 1 may also be 0.1 mm or more and 3.0 mm or less, or 0.1 mm or more and 2.5 mm or less. 【0034】 The shape of the cross-section 2 of the copper alloy wire 1 is not particularly limited. The cross-section 2 is a cross-section perpendicular to the longitudinal direction of the copper alloy wire 1. In this example, the shape of the cross-section 2 is circular, as shown in Figure 2. In this example, the copper alloy wire 1 is a round wire, as shown in Figure 1. The shape of the cross-section 2 may also be elliptical or polygonal. A polygonal shape could be a square or a hexagon. When the copper alloy wire 1 is a round wire, the shape of the cross-section 2 is circular, and the wire diameter 1d of the copper alloy wire 1 is its diameter. When the shape of the cross-section 2 is elliptical or polygonal, the wire diameter 1d is the diameter of a circle having an area equal to the area of ​​the cross-section 2. 【0035】 <<Center and Outer Periphery>> As shown in Figure 2, the cross-section 2 comprises a center 3 and an outer peripheral 4. The center 3 is the interior of a circle with a radius of 3r that is 1 / 8 of the wire diameter 1d, centered on the central axis of the copper alloy wire 1. The outer peripheral 4 is the region of the cross-section 2 other than the center 3. The outer peripheral 4 is the ring-shaped interior enclosed by the outer edge of the center 3 and the outer edge of the cross-section 2. In Figure 2, for clarity, the boundary between the center 3 and the outer peripheral 4 is shown by a dashed line. 【0036】The GROD value of the central part 3 measured by the electron backscatter diffraction method is 23° or less. Since the GROD value of the central part 3 of the copper alloy wire 1 is 23° or less, the central part 3 is not embrittled, and the copper alloy wire 1 has excellent mechanical properties over its entire length. The copper alloy wire 1 with the GROD value of the central part 3 being 23° or less is manufactured without wire breakage occurring during the manufacturing process as shown in the test examples described later. The copper alloy wire 1 with the GROD value of the central part 3 being 23° or less is manufactured by performing wire drawing on a cast wire rod with the GROD value of the central part being 23° or less. When the GROD value exceeds 23°, the residual strain is large, and the location where the residual strain accumulates is embrittled. When wire drawing is performed on a cast wire rod with a GROD value exceeding 23° and a processed material obtained by processing the cast wire rod, wire breakage is likely to occur starting from the location where the residual strain accumulates. In other words, since no wire breakage occurred even when wire drawing was performed on a cast wire rod with the GROD value of the central part being 23° or less, the copper alloy wire 1 with the GROD value of the central part 3 being 23° or less is obtained. The GROD value of the central part 3 may be 20° or less, 18° or less, 15° or less, 12° or less, or 11° or less. 【0037】 The GROD value of the outer peripheral part 4 measured by the electron backscatter diffraction method is, for example, 23° or less. In a cast wire rod, when the GROD value of the outer peripheral part 4 is 23° or less, wire breakage is unlikely to occur even when wire drawing is performed. Therefore, the copper alloy wire 1 obtained by performing wire drawing on this cast wire rod also has a GROD value of the outer peripheral part 4 of 23° or less, and its mechanical properties are likely to be high. The GROD value of the outer peripheral part 4 may be 20° or less, 18° or less, 15° or less, 12° or less, or 11° or less. 【0038】 The GROD value of the central part 3 and the GROD value of the outer peripheral part 4 may be the same or different. The GROD value of the central part 3 may be smaller or larger than the GROD value of the outer peripheral part 4. 【0039】The outer surface 5 of the copper alloy wire 1 has, for example, processing marks (not shown). The presence of processing marks on the outer surface 5 of the copper alloy wire 1 indicates that the copper alloy wire 1 was obtained by performing a corresponding process on a cast wire. The processing marks are, for example, wire drawing marks. The wire drawing marks are formed in a streaky manner, extending along the longitudinal direction of the copper alloy wire 1. The copper alloy wire 1 is manufactured by drawing a cast wire. The copper alloy wire 1 may also be manufactured by drawing a wire that has been rolled from a cast wire. 【0040】 <Tensile Strength> The tensile strength of copper alloy wire 1 is, for example, 250 MPa or more. Copper alloy wire 1 with a tensile strength of 250 MPa or more has excellent strength. The tensile strength can be measured according to JIS Z 2241:2011. The tensile strength may be 260 MPa or more, or 270 MPa or more. The tensile strength may be 1200 MPa or less from the viewpoint of balancing with conductivity, etc. 【0041】 <Elongation> A copper alloy wire 1 with a GROD value of 23° or less in the central part 3 has more than 10% greater elongation than, for example, a copper alloy wire 1 with a GROD value of more than 23° in the central part 3. 【0042】 <Method for Manufacturing Copper Alloy Wire> The copper alloy wire 1 described above can be manufactured through a casting process to produce a cast wire made of copper alloy, and a wire drawing process to draw the cast wire. Figure 3 shows an example of a cast wire 10. 【0043】 ≪Casting Process≫ In the casting process, cast wire 10 is produced by intermittent continuous casting of molten copper alloy. The copper alloy has the same composition as the copper alloy wire 1 described above. Continuous casting can be, for example, top-draw casting, vertical casting, or horizontal casting. In top-draw casting, the end of a cylindrical mold is placed inside the molten metal, and the solidified wire inside the mold is pulled upwards towards the top of the mold to produce the cast wire 10. Intermittent continuous casting is a method in which the casting wire 10 is repeatedly drawn out and stopped. 【0044】The ratio S1 / ST of the time for one draw S1 (sec) to the total time ST of one stop S2 (sec) is, for example, 0.68 or less. The wire diameter x (mm) of the cast wire 10 and the casting speed y (mm / sec) of the cast wire 10 satisfy, for example, y ≤ 155 / x. The casting speed y is the value obtained by dividing the length of one cast wire 10 produced by the time required to produce one cast wire 10. That is, the casting speed y is the value obtained by dividing the length of the cast wire 10 by the total time of all draw S1 and all stop S2. By having a ratio S1 / ST of 0.68 or less and satisfying y ≤ 155 / x, it is easy to produce a cast wire 10 with a cast structure angle of 70° or less, as described later. Cast wire rods 10 with a cast structure angle of 70° or less are more likely to satisfy a GROD value of 23° or less in the center. 【0045】 The ratio S1 / ST may be 0.63 or less, or 0.58 or less. The lower limit of the ratio S1 / ST is not particularly limited. The ratio S1 / ST may be 0.05 or more, 0.10 or more, or 0.15 or more. That is, the ratio S1 / ST may be 0.05 or more and 0.68 or less, 0.10 or more and 0.63 or less, or 0.15 or more and 0.58 or less. The wire diameter x is, for example, 5 mm or more and 25 mm or less. The wire diameter x may be 6 mm or more and 24 mm or less, or 7 mm or more and 23 mm or less. The casting speed y is, for example, 1.67 mm / sec or more and 30 mm / sec or less. The casting speed y may be 2 mm / sec or more and 28 mm / sec or less, or 2.5 mm / sec or more and 25 mm / sec or less. 【0046】 The acceleration of the cast wire 10 from a stationary state to the withdrawal speed is, for example, 100 mm / sec. ２ 4000mm / sec or more ２ The following applies: The drawing speed is the value obtained by dividing the length of the cast wire 10 by the total time S1 for all drawing. The above acceleration is 100 mm / sec. ２ 4000mm / sec or more ２ The following conditions make it easier to manufacture a cast wire rod 10 with a cast structure angle of 70° or less, as described below. A cast wire rod 10 with a cast structure angle of 70° or less is more likely to satisfy a Grod value of 23° or less at its center. The above acceleration is 200 mm / sec.２ Above 3000 mm / sec ２ or less, or 300 mm / sec ２ Above 2000 mm / sec ２ or less may also be used. 【0047】 The deceleration from the above drawing speed until the casting wire 10 stops is, for example, 100 mm / sec ２ or more. When the above deceleration is 100 mm / sec ２ or more, it is easy to manufacture the casting wire 10 with a casting structure angle of 70° or less described later. The casting wire 10 with a casting structure angle of 70° or less is likely to satisfy a GROD value of 23° or less at the center. The above deceleration is 150 mm / sec ２ or more, or 200 mm / sec ２ or more may also be used. The above deceleration is, for example, 2000 mm / sec ２ or less, 1500 mm / sec ２ or less, or 1000 mm / sec ２ or less. That is, the above deceleration is 100 mm / sec ２ above 2000 mm / sec ２ or less, 150 mm / sec ２ above 1500 mm / sec ２ or less, or 200 mm / sec ２ above 1000 mm / sec ２ or less may also be used. 【0048】 In the casting process, by making the ratio S1 / ST and the acceleration constant within the above ranges and repeating the drawing and stopping of the casting wire so that the deceleration becomes 100 mm / sec ２ or more, it is easy to satisfy a GROD value of 23° or less at the center. 【0049】 The casting structure angle is obtained as follows. As shown in FIG. 3, a longitudinal section of the casting wire 10 is taken. The longitudinal section is a section passing through the center of the casting wire 10 and along the axis of the casting wire 10. The longitudinal section is taken so that the length between the upper side 21 and the lower side 22 of the longitudinal section is the wire diameter x. In the longitudinal section of FIG. 3, the direction of the white arrow from left to right on the paper is the traveling direction of the casting wire 10. 【0050】An upper parallel line 31 is drawn parallel to the upper side 21, passing through a point 1 / 4 times the line diameter x from the upper side 21 towards the lower side 22 of the vertical section. Five upper reference points 51 are drawn at 6 mm intervals along the upper parallel line 31, from the left side 23 towards the right side 24. A lower parallel line 32 is drawn parallel to the lower side 22, passing through a point 1 / 4 times the line diameter x from the lower side 22 towards the upper side 21 of the vertical section. Five lower reference points 52 are drawn at 6 mm intervals along the lower parallel line 32, from the left side 23 towards the right side 24. The five upper reference points 51 are designated as the 1st to 5th upper reference points 51, in order from left to right. The five lower reference points 52 are designated as the 1st to 5th lower reference points 52, in order from left to right. 【0051】 An upper crossing line 41 is formed that follows the grain boundary and intersects the upper parallel line 31. A lower crossing line 42 is formed that follows the grain boundary and intersects the lower parallel line 32. In any of the continuous casting methods described above, the grain boundaries are formed such that they are inclined from the axis of the cast wire 10 toward the upper edge 21 or lower edge 22 as the cast wire 10 moves toward the direction of travel. This is because the cast wire 10 is manufactured by cooling the molten metal in contact with the mold sequentially from the outer surface toward the center and sequentially from the front toward the back in the direction of travel of the molten metal. The upper crossing lines 41 and lower crossing lines 42 are lines that are inclined toward the upper edge 21 or lower edge 22 as the cast wire 10 moves toward the direction of travel, as shown in Figure 3. In Figure 3, for the sake of explanation, seven upper crossing lines 41 and six lower crossing lines 42 are shown. The seven upper crossing lines 41 are designated as the first to seventh upper crossing lines 41, from left to right. The six lower crossing lines 42 are designated as the 1st to 6th lower crossing lines 42, in order from left to right. 【0052】On the upper parallel lines 31, find the smaller angle θ between each of the upper crossing lines 41 that is closest to each of the first to fifth upper reference points 51 and the upper parallel lines 31. That is, in Figure 3, find the smaller angle θ between each of the second upper crossing line 41, the fourth upper crossing line 41, the fifth upper crossing line 41, the sixth upper crossing line 41, and the seventh upper crossing line 41 and the upper parallel lines 31. On the lower parallel lines 32, find the smaller angle θ between each of the lower crossing lines 42 that is closest to each of the first to fifth lower reference points 52 and the lower parallel lines 32. That is, in Figure 3, find the smaller angle θ between each of the second lower crossing line 42, the third lower crossing line 42, the fourth lower crossing line 42, the fifth lower crossing line 42, and the sixth lower crossing line 42 and the lower parallel lines 32. The average of the ten angles θ obtained is the casting microstructure angle. 【0053】 In Figure 3, for the sake of explanation, an example is shown in which there is no upper crossing line 41 passing through the upper reference point 51. However, if there is an upper crossing line 41 passing through the upper reference point 51, then the upper crossing line 41 passing through the upper reference point 51 is the upper crossing line 41 that is closest to the upper reference point 51. The same applies to the lower crossing line 42, which is closest to the lower reference point 52. In Figure 3, near the second upper reference point 51, there is a third upper crossing line 41 located to the left of the second upper reference point 51 and a fourth upper crossing line 41 located to the right. Here, on the upper parallel line 31, the distance between the second upper reference point 51 and the fourth upper crossing line 41 is shorter than the distance between the second upper reference point 51 and the third upper crossing line 41. Therefore, we find the smaller of the angles θ between the fourth upper intersecting line 41 and the upper parallel line 31, but we do not find the smaller of the angles θ between the third upper intersecting line 41 and the upper parallel line 31. 【0054】≪Wire Drawing Process≫ In the wire drawing process, the cast wire rod 10 is subjected to wire drawing. The degree of wire drawing can be appropriately selected according to the wire diameter x of the cast wire rod 10 and the wire diameter 1d of the copper alloy wire 1 after wire drawing. The degree of wire drawing is, for example, 0.1 to 12.0, 0.2 to 11.0, or 0.3 to 10.0. The degree of wire drawing is the absolute value expressed as a natural logarithm of the ratio of the cross-sectional area of ​​the wire rod before drawing to the cross-sectional area of ​​the wire rod after drawing. Wire drawing is performed using, for example, a die conforming to the AWG (American Wire Gauge) standard. 【0055】 In the wire drawing process, the wire rod obtained by rolling the cast wire rod 10 may also be subjected to wire drawing. 【0056】 Cast wire rods 10 with a central GROD value of 23° or less are less prone to breakage during wire drawing. Therefore, copper alloy wires 1 obtained by drawing cast wire rods 10 with a central GROD value of 23° or less are less prone to breakage during the manufacturing process and have excellent productivity. 【0057】 <Copper Alloy Stranded Wire> The copper alloy wire 1 of the embodiment can be used as a strand in a copper alloy stranded wire 120, as shown in Figure 4. The copper alloy stranded wire 120 is made by twisting together multiple copper alloy wires 1. Compared to a single copper alloy wire 1 having the same cross-sectional area, the copper alloy stranded wire 120 has superior flexibility, and each strand is less likely to break even when subjected to impact and repeated bending. Therefore, the copper alloy stranded wire 120 has excellent impact resistance and fatigue properties. Figure 4 illustrates a copper alloy stranded wire 120 with seven concentric strands, but the number of strands of copper alloy wire 1 and the twisting method can be changed as appropriate. 【0058】 The copper alloy stranded wire 120 can be a compressed stranded wire, which is formed by compression molding after twisting. Compressed stranded wire has excellent stability in the twisted state. Furthermore, compressed stranded wire tends to have better mechanical properties than simply twisted wire and can be made in a smaller diameter. 【0059】<Insulated Wire> The copper alloy wire 1 or the copper alloy stranded wire 120 of the embodiment can be used as a conductor for electric wires. The insulated wire 100 of the embodiment comprises a conductor 110 and an insulating layer 130, as shown in Figure 4. The conductor 110 comprises a copper alloy stranded wire 120. The insulating layer 130 covers the outer circumference of the conductor 110. The insulated wire 100 has excellent impact resistance and fatigue characteristics because it comprises a conductor 110 made of a copper alloy stranded wire 120 which has excellent impact resistance and fatigue characteristics. As an alternative example of the insulated wire 100, the conductor 110 may be a single-strand copper alloy wire 1. 【0060】 The insulating material forming the insulating layer 130 can be appropriately selected. Examples of insulating materials include polyvinyl chloride (PVC), non-halogen resins, and materials with excellent flame retardancy. Known insulating materials can be used. The thickness of the insulating layer 130 can be appropriately selected within a range that provides a predetermined insulating strength. 【0061】 <Wire with Terminal> The insulated wire 100 of this embodiment can be used as a wire for various applications, such as wire harnesses mounted on equipment such as automobiles or airplanes, wiring for various electrical equipment such as industrial robots, and wiring for buildings. When used in wire harnesses, typically a terminal portion 210 is attached to the end of the insulated wire 100. As shown in Figure 5, the wire with terminal 200 of this embodiment comprises the insulated wire 100 of this embodiment and a terminal portion 210 attached to the end of the insulated wire 100. This wire with terminal 200 has excellent impact resistance and fatigue characteristics because it is equipped with an insulated wire 100 which has excellent impact resistance and fatigue characteristics. In Figure 5, a crimp terminal is shown as the terminal portion 210, which has a female or male mating portion 212 at the first end, an insulation barrel portion 213 attached to the insulating layer 130 at the second end, and a wire barrel portion 211 attached to the conductor 110 in the middle. The crimp terminal is crimped to the end of the conductor 110, which is exposed at the end of the insulated wire 100 after the insulating layer 130 has been removed, thereby connecting the conductor 110 electrically and mechanically. In addition to crimp terminals and other crimp-type terminals, the terminal portion 210 may also be connected by melting the conductor 110. 【0062】[Test Example] A cast wire made of copper alloy was prepared, and the presence or absence of wire breakage was investigated when this cast wire was subjected to wire drawing. 【0063】 <Samples> For all of the samples, Sample No. 1, Sample No. 2, Sample No. 3, Sample No. 11, and Sample No. 12, cast wire rods were produced by intermittent continuous casting of molten copper alloy, and these cast wire rods were then drawn to produce drawn wire rods. 【0064】 In each sample, the molten copper alloy has a composition containing iron, phosphorus, and tin, with the remainder being copper and unavoidable impurities. The proportion of each element contained in the molten metal of each sample is as shown in the composition in Table 1. The cast wires of each sample were manufactured by intermittent top-draw continuous casting. The length of the cast wire was 50 m. The wire diameter (mm), casting speed (mm / sec), ratio of the time of one draw S1 (sec) to the total time ST of one draw S1 (sec) and one stop S2 (sec), and acceleration (mm / sec) from the stopped state to the draw speed of the cast wire are specified. ２ ), and the deceleration (mm / sec) from the above-mentioned drawing speed until the cast wire stops. ２ The results are as shown in Table 1. In this example, the ratio S1 / ST and acceleration were kept constant, while the deceleration was varied. For samples No. 1 to No. 3, the casting speed y and the wire diameter x of the cast wire satisfy y ≤ 155 / x. 【0065】 Each drawn wire was manufactured by drawing the prepared cast wire. The degree of drawing and the final wire diameter (mm) of the manufactured drawn wire are shown in Table 2. 【0066】 【0067】 <Casting Microstructure Angle> The casting microstructure angle (°) of the cast wire for each sample was determined. The method for determining the casting microstructure angle is as described above, referring to Figure 3. The results of the casting microstructure angle are shown in Table 1. The values ​​shown in Table 1 are rounded to the nearest tenth. 【0068】<Component Analysis> The composition of each drawn wire sample was investigated by mapping analysis using an electron beam microanalyzer (EPMA). As a result, the composition of each drawn wire sample was the same as the composition of the molten copper alloy. In other words, the composition of each drawn wire sample was as shown in Table 1. 【0069】 <GROD Value> The crystal orientation was measured in the cross-section of the drawn wire of each sample by electron beam backscatter diffraction. The GROD value of the center was determined from the crystal orientation map obtained from multiple measurement points. Specifically, points with a reliability index (CI) value of less than 0.1 were excluded, and boundaries where the orientation difference between adjacent measurements was greater than 15° were considered as grain boundaries, and measurements were taken in steps of 1 / 10 or less of the average grain size. The results are shown in Table 2. 【0070】 <Tensile Strength> The tensile strength of each drawn wire sample was measured according to JIS Z 2241:2011. Specifically, a sample of each material was prepared, and a tensile test was performed with a gripping distance of 200 mm and a tensile speed of 20 mm / min until the sample broke. The tensile strength was calculated by dividing the maximum load value during this tensile test by the area of ​​the cross-sectional surface of the sample. The results are shown in Table 2. 【0071】 <Presence or absence of wire breakage during wire drawing> We investigated whether or not wire breakage occurred during the wire drawing process for each sample. The results are shown in Table 2. In the "No breakage" column of Table 2, "None" means that the drawn wire was manufactured without any wire breakage. "Yes" means that wire breakage occurred. 【0072】 【0073】In the drawn wires of samples No. 1 to No. 3, no breakage occurred during the drawing process. In the drawn wires of samples No. 1 to No. 3, the GROD value at the center was 23° or less. In the cast wires of samples No. 1 to No. 3, the cast structure angle was 70° or less, and it is thought that the GROD value at the center was 23° or less. By performing the drawing process on cast wires with a GROD value at the center of 23° or less, it was possible to perform the drawing process without breakage, and it is thought that drawn wires with a GROD value at the center of 23° or less were produced. All of the drawn wires of samples No. 1 to No. 3, which did not break during the drawing process, are thought to have excellent mechanical properties when used as drawn wires. 【0074】 In the drawn wires of sample No. 11 and sample No. 12, wire breakage occurred during the wire drawing process. In the drawn wires of sample No. 11 and sample No. 12, the GROD value at the center was greater than 23°. In the cast wires of sample No. 11 and sample No. 12, the cast structure angle was greater than 70°, and it is thought that the GROD value at the center was greater than 23°. When the GROD value at the center is greater than 23°, the residual strain at the center of the cast wire is large, and the area where this residual strain has accumulated is brittle. Therefore, it is thought that when a cast wire with a cast structure angle greater than 70° and a GROD value at the center greater than 23° was subjected to wire drawing, wire breakage occurred starting from the area where the residual strain had accumulated. 【0075】 1 Copper alloy wire 2 Cross section 3 Center section 4 Outer section 5 Outer surface 1d Wire diameter 3r Radius 3L Length 10 Cast wire 21 Top edge, 22 Bottom edge, 23 Left edge, 24 Right edge 31 Upper parallel lines, 32 Lower parallel lines 41 Upper crossing lines, 42 Lower crossing lines 51 Upper reference point, 52 Lower reference point x Wire diameter θ Angle 100 Insulated wire 110 Conductor, 120 Copper alloy stranded wire, 130 Insulation layer 200 Wire with terminal 210 Terminal section, 211 Wire barrel section 212 Mating section, 213 Insulation barrel section

Claims

1. A copper alloy wire having a composition consisting of a copper alloy containing 0.05% to 1.60% by mass of iron, 0.01% to 0.70% by mass of phosphorus, and 0.05% to 0.70% by mass of tin; a wire diameter of 0.1 mm to 15.0 mm; and a cross-section having a central part and an outer periphery, wherein the GROD value of the central part measured by electron beam backscatter diffraction is 23° or less.

2. The copper alloy wire according to claim 1, wherein the central part is the interior of a circle with a radius of 1 / 8 of the wire diameter, centered on the central axis of the copper alloy wire.

3. The copper alloy wire according to claim 1 or 2, wherein the outer periphery is a region other than the central part, and the GROD value of the outer periphery measured by electron beam backscatter diffraction is 23° or less.

4. The copper alloy wire according to any one of claims 1 to 3, wherein the outer surface of the copper alloy wire has processing marks.

5. A copper alloy wire according to any one of claims 1 to 4, wherein the tensile strength is 250 MPa or more.

6. A stranded copper alloy wire comprising a plurality of copper alloy wires according to any one of claims 1 to 5, twisted together.

7. A covered electric wire comprising a conductor and an insulating layer covering the outer circumference of the conductor, wherein the conductor comprises the copper alloy stranded wire described in claim 6.

8. A wire with a terminal, comprising a covered wire as described in claim 7 and a terminal portion attached to the end of the covered wire.

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