TWI327173B - - Google Patents

Description

1327173 IX. Description of the Invention: [Technical Field] The present invention relates to a copper alloy which has excellent strength, electrical conductivity and bending workability and is suitable for electrical and electronic parts such as terminals, connectors, switches and relays. [Prior Art] Various terminals, connectors, relays, switches, etc. for electrical and electronic equipment use inexpensive brass for applications that emphasize manufacturing costs. Further, the use of phosphor bronze is emphasized for applications where elasticity is emphasized, and nickel-silver alloys are used for applications where flexibility and corrosion resistance are emphasized. These copper alloys are solid solution-strengthened alloys, which can improve strength and elastic properties due to the action of alloying elements, but have low electrical and thermal properties. On the other hand, in recent years, in place of a solid solution-strengthened alloy, the amount of precipitation-strengthened copper alloy is increasing. The characteristics of precipitated reinforced copper alloy are

Thus, the alloying elements are precipitated as fine compound particles in the Cu matrix. When the alloy element is precipitated, the strength rises and the conductivity increases. Therefore, the strengthening: the copper alloy 'can be made to have a higher electrical conductivity than the solid solution strengthening alloy at the same strength. Precipitation-enhanced copper alloy, #Cu~Ni—Si-based alloy, Cu-Be-based alloy, Cu-Ti-based alloy, Cu-Zr-based alloy 々 However, in the precipitation-strengthened alloy, it is necessary to fix the alloying elements first. The high-temperature, short-time heat treatment (solution treatment) in the CU and the low-temperature, long-time heat treatment (aging treatment) for precipitating the alloy bismuth are complicated in the production steps. In addition, people 4 Benshan·, «金兀素, because of the inclusion of Si, Ti 'zr, Be, etc. 1327173 wins, & difficult to control the quality of the cast bond. Therefore, the production cost of the precipitation-strengthened alloy is much higher than the manufacturing cost of the solid solution-reinforced alloy. In recent years, with the miniaturization of H parts of electronic machines, terminals, connectors, switches, and electric appliances have also been miniaturized, and the cross-sectional area of the energized portion of the copper alloy has also changed. The amount of hair will be =. As long as a copper alloy having a higher conductivity is used, the increase in the amount of heat generation can be suppressed. When a conventional solid solution-strengthened alloy is used, "if a copper port having a high conductivity is selected, the strength is low", so that the contact force is insufficient at the electrical contact, and if a precipitation-strengthened alloy is used, it may not be used. Make strong ^ + - the cost will be ambiguous. Since the market demand for copper alloys is very strict, it is difficult to tolerate cost increases. In the above, JL researched to develop a solid solution-strengthened alloy to develop a Cu-Zn alloy represented by a sufficient amount of conductive steel, and to manufacture a copper alloy 1 system. Heyi, coupled with the cheap price of Zn, is characterized by a low-cost alloy. In order to expand the electronic component materials, it is expected that the electronic component materials can be expanded. Patent Document 2 and Patent Document 3 disclose a copper alloy in which Sn is added to the patent document. The seed is added to the Cu-Zn alloy. Patent Document i: Japanese Patent Laid-Open No. 162737. Patent Document 2: Japanese Patent Laid-Open No. Hei. No. 4 publication. Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 7-258777. SUMMARY OF THE INVENTION However, the c Zn_Sn alloy disclosed in the documents does not have

1JZ/1tJ combines a good guide car and a miniaturized component. It is impossible to respond to the electronic probability of Γ: Γ, is to provide a sufficient conductive alloy at the same time. The inventors of the present invention have reduced the size of the zn of the Sn* sleeve Du-Zn D gold of the Cu-7, and added less::S: and adjusted the metal structure, A copper alloy having a desired sufficient electrical conductivity, strength, and testability is obtained. That is, the present invention provides: () A copper alloy for electric and electronic equipment characterized by containing 2 to 12% by mass of Zn and ϋ ϋ / / , , , , , , , , ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The relationship between the mass % of Zn and the cost of Zn, “0/buy s % / agronomy ([% Zn]) is adjusted to the range of formula (1). The remainder is composed of copper and unavoidable impurities. Avoid the impurities s > the degree of agriculture is less than 3G f amount ~ the agricultural degree is π mass below PPm, and has a conductivity of 35% 1 milk or more and (4) the tensile strength above the hidden 'can be parallel direction (bending axis and The direction in which the rolling direction is parallel) and the orthogonal direction (the direction in which the arc is orthogonal to the rolling direction) is closely combined with the bending process. 〇-5^[%Sn]+〇.16[%Zn]^2.〇... (1) (2) The copper alloy for electric and electronic equipment according to the above (!), which contains Ni, Mg, Fe, P, Mn, Co, Be in a total range of 0 005 to 0 5 % by mass.

Ti, Cr, Zr, A1 and Ag t are more than one type of element. (3) The copper alloy for electric and electronic equipment according to (i) to (2) above, the length of the cross section parallel to the rolling direction and the thickness direction exceeds 5〇μηη/173 • the number of cool impurities , 0.5 or less. (4) The copper alloy for electric and electronic equipment according to the above (1) to (2), wherein the crystal grains constituting the metal structure in the metal structure parallel to the cross section of the rolling surface have a shape stretched in the rolling direction. Further, when the average particle diameter of the crystal grains in the direction orthogonal to the rolling direction is a, and the average particle diameter in the direction parallel to the rolling direction is b, the following dimensions are obtained, a = 1.0 ΙΟ. Ο μιη, preferably For i 〇~5 〇μιη b / a = 1, 2~2_5. (5) The copper alloy for electric and electronic equipment according to (1) to (2) above, wherein the X-ray diffraction intensities obtained from the (2 〇〇) plane and the (220) plane of the rolling surface are luoq and The x-ray diffraction intensity obtained from the (2 〇〇) plane and the (22 〇) plane of the copper powder was 1, respectively. (_) and Iq (22G), - 0.23 1 (200) / I 〇 (2 〇〇) S 1.0 - 2.0$ 1 (22.) / 1. (22.) $5.0. (6) A method for producing a copper alloy for an electric and electronic device, for manufacturing the copper alloy for electric and electronic equipment according to (1) to (5), wherein the following steps are carried out in sequence: ~ΙΟμιη; 1 〜1 Ομηι, A. Intermediate recrystallization annealing, processing grain size into i B. intermediate cold rolling of 35~9〇% of processing degree; c. final recrystallization annealing, processing grain size to preferably 1~5 μπι; D. Finishing degree 15~6〇% of the final cold rolling. According to the present invention, it is possible to manufacture a copper alloy which has sufficient conductivity and strength as required and which can be miniaturized in response to electronic equipment parts. 1327173 [Embodiment] The present invention recognizes that sufficient characteristics are required as described below. (A) Conductivity • V^IACS or higher, this conductivity is comparable to that of the Cu—Ni—Si alloy (Carson Alloy) of the precipitation strengthened alloy. Further, the conductivity of brass (C2600) was 28% IACS, and the conductivity of phosphor bronze (C521〇) was 13% IACS. (B) Tensile strength: 410 MPa or more. This tensile strength is equivalent to the two-strength strength of the grade H of brass (C26〇〇) prescribed by JIS (JISH3100). (c) F-curve workability: 18 〇 * degree close bending can be performed in the orthogonal direction and the parallel direction. In this bending test, if no cracks or severe surface wrinkles occur, the most stringent grade of the fastener can be processed. That is, the copper alloy provided by the present invention has the strength of brass, the conductive yttrium of 'card 35 y gold, and the processing property equivalent to that of brass or cassin alloy, and can be applied to miniaturization and continuous progress. Electronic machine parts materials. In the conventional CU-Zn-Sn alloy, there is no alloy satisfying the above (4) (B) (C) food portion. For example, the alloy disclosed in Patent Document 3 satisfies (B), but since the structural control (inclusion classification, grain shape, crystal orientation, etc.) required for (C) is not performed, Therefore, the f-mechanical system R/t=〇.8 is 9 degrees, the curvature is the radius of the curve, and t is the thickness of the sample. Here, the outline of the above two types of bending test methods is as shown by the circle i. In the present invention, in order to obtain the above characteristics, the composition of the alloy of the present invention, the 1327173 structure and the production method are defined as follows. (1) Ζη and Sn concentration The copper alloy of the present invention has 211 and Sn as basic components, and the range of mechanical properties βΖη concentration and concentration is controlled by the action of two elements, respectively, 2 to 12% by mass and qm" If the amount is less than 2%, the Cu-Zn alloy is inferior in manufacturability. If it exceeds 12%, the desired conductivity cannot be obtained even if the Sn concentration is adjusted. In the case of Zn, it is preferable to control Zn to 7 mass%, and when importance is emphasized, it is preferable to make Zn more than 7% by mass.

Sn has a function of promoting work hardening at a pressure delay, and if sn is less than 〇1%, the strength is insufficient. The other side - if Sn exceeds 〇1%, it will reduce the manufacturability of the alloy.

The total concentration (τ) of Sn and Zn was adjusted as follows. 0.5^ 2.0 T= [%Sn]+ 0.16[%Ζη] Here, [%811] and [%211] are the mass% concentrations of Sn and Ζn, respectively. When the enthalpy is 2.0 or less, a conductivity of 35% IACS or more can be obtained. Further, when T is made 0.5 or more, a tensile strength of 410 MPa or more can be obtained by appropriately adjusting the metal structure. Therefore, τ is defined as 〇 5 to 2 〇. More preferably, the range of T is from 1.0 to 1.7'. By adjusting to this range, a more stable conductivity of 35% IACS or more and a tensile strength of 41 MPa or more can be obtained. (2) Ni, Mg, Fe, P, Mn, Co, Be, Ti, Cr, Zr, A1 Ag 1327173 In the alloy of the present invention, in order to improve the strength, heat resistance, stress relaxation resistance, etc. of the alloy, a total of 0.005 may be added. 〇. 5 mass% of one or more of Ni, Mg, Fe, P, Μη, Co, Be, Ti, Cr, Zr, A1 and Ag. However, since the addition of the alloying element causes a decrease in electrical conductivity, a decrease in manufacturability, and an increase in raw material cost, it is necessary to take this into consideration. If the total amount of the above elements is less than 0.005% by mass, the lifting property cannot be exhibited. effect. On the other hand, when the total amount of the above elements exceeds 5% by mass, the electrical conductivity is remarkably lowered. Therefore, the total amount is defined as 〇〇〇5 to 〇·5 mass%. (3) Number of inclusions, S concentration, and agronomic degree The cross section parallel to the rolling direction and parallel to the thickness direction was observed, and the number of inclusions having a length exceeding 50 μm was limited to 〇5/claw 2 or less. When the inclusions exceed 0.5/mm2, the bending workability is remarkably lowered, and the 180-degree adhesion bending cannot be performed. In order to adjust the inclusions to the above range, the concentrations of 3 and cerium are set to 30 ppm by mass or less and 5 Å by mass or less, respectively. If the s or strontium concentration exceeds this range, the inclusions will exceed 个5/mm2. (4) Crystal grain shape If the metal structure of the alloy of the present invention parallel to the cross section of the calendering surface was observed, it was observed that the (4) crystal grains were stretched in the rolling direction. If the average particle diameter of the crystal grains in the direction orthogonal to the desired direction is a, and the average particle diameter in the direction parallel to the direction of the desired direction is b, the a value and the b/a value and the strength of the alloy and the f-curve processing The sex dependence β can therefore be used as a parameter to adjust the properties of the alloy. 11 1327173 If the person 3 is lower than ιμπι, the bending workability is lowered and the i8 twist tightness bending cannot be performed. a If the strength exceeds 1 〇μΐη, the strength is lowered and it is difficult to obtain a tensile strength of 4 〇Μ & & and above, and bending is performed. The curved portion produces a severe surface sensation. Therefore, a is defined as (7) (four) and better (iv). When b/a exceeds 2.5, the bending workability is lowered and the 18-degree tight bending cannot be performed. If b/a is less than 丨2, the strength is lowered and it is difficult to obtain a tensile strength of 41 MPa or more. Therefore, b/a is defined as 12 to 25. Further, in the case where the microstructure is not completely recrystallized at the time of final annealing, the calendered structure remains. When the degree of processing of the final cold rolling is very high, the deformation of crystal grains is remarkable and it is difficult to measure b/a. The alloy having such a structure has extremely poor bending workability and cannot be bent at 180 degrees. (5) Crystal orientation of the calendering surface By X-ray diffraction by the rolling surface of the copper alloy, the degree of integration of the (200), (220), (111), and (31) planes of the calendering surface can be obtained. In the case of the alloy of the present invention, the degree of integration of the (200) plane and the (220) plane is correlated with the strength and bending workability of the alloy. Therefore, these characteristics can be used as parameters to adjust the properties of the alloy. The X-ray diffraction intensities obtained from the (200) and (220) faces of the alloy rolling surface are I (2QQ) and Ι (22 ϋ), respectively, and the X (200) and (220) faces of the copper powder are obtained. The ray diffraction intensities were respectively 1 〇 (22 ()), and the integration degree of each surface was evaluated by the ratio of I to 1 ( (1/IG). Here, the copper powder is obtained by using a standard sample of a random orientation, and by dividing the diffraction intensity (I) of the sample by the diffraction intensity (1 〇) of the copper powder, it is not affected by the apparatus or the measurement conditions. The value of the normalized integration. 12 1327173 If bow/ ΐίκ2. . } When it exceeds 1.0, it is 18 degrees in the orthogonal direction. When f is tight, the surface of the f-surface is greatly reduced. On the other hand, if it is 2 〇 2 lower, the surface wrinkles of the curved surface become larger when the 180-degree close bending is performed in the parallel direction. Therefore, 1 (200 〆 10 (2 〇〇) is defined as 0 〇. If Iopw is less than 2.0, the strength is lowered and it is difficult to obtain a tensile strength of 4H) MPa or more. On the other hand, if the thickness exceeds 5 (), the bending workability is lowered and the 18-degree tightness bending cannot be performed. Therefore, ^2 will be. 〆 1〇 (22.) is specified as 2.0~5.0.

(6) Manufacturing method The alloy of the present invention is subjected to the following steps in order to be processed into a material for an electric electronic device. (A) Intermediate recrystallization annealing: The grain size is adjusted to 1 to 1 〇^m. (Β) Intermediate cold rolling: processing degree 35~9〇%. (C) Final recrystallization annealing: The grain size is adjusted to i~i, preferably 1 to 5 μm. (D) Final cold rolling: processing degree 15~60%. Here, the degree of processing R is defined by the following formula. R~~ (t()—t)/ toGo: thickness before rolling, t: thickness after rolling) If the final cold rolling processing degree is less than 15%, b/a will be lower than 丨·2, and 1 ( 22 ()) / screaming will be lower than 2.0. On the other hand, if the degree of final cold rolling is more than 60%, b/a will exceed 2.5, and I(22.) / IG(22.) will exceed 5.0. Therefore, the processing degree of the final cold rolling is specified to be 15 to 6 %. If the grain size of the final annealing is less than 1 μπι, then a is less than 1 μηη. Another 'if the grain size of the final annealing exceeds 10 μm, then a exceeds i (^m. 13 1327173 Therefore 'the grain size of the final annealing is specified to be 1 to ΙΟμιη, preferably 1 to 5 μπι 〇 intermediate cold rolling If the degree of processing is less than 35% ', then Ι(200) / 10(200) will be lower than 0_2. On the other hand, if the intermediate cold rolling process exceeds 90%, 1(200) / 10(200) will exceed 1 Therefore, the processing degree of the intermediate cold rolling is specified to be 35 to 90%. If the grain size of the intermediate annealing is lower than Ιμιη, 1 (2 (10)) / 1 〇 (2 () ()) will exceed 1.0. On the other hand, if the grain size of the intermediate annealing exceeds 1 〇μηι, then a /1〇(2〇()) will be lower than 0.2 » Therefore, the grain size of the intermediate annealing is specified to be 1~1〇 Μχη. Further, after the final cold rolling, in order to improve the elastic limit value, the stress corrosion tortoise, the crack sensitivity, the stress relaxation resistance, etc., the strain relief annealing is performed, and the above-mentioned effects of the present invention can be similarly obtained. On the surface of the final cold rolling, 'plating by soldering tin plating, etc.', as long as the thickness of the plating layer is within 5 μm, the same can be obtained on the surface of the present invention. [Examples] 2 kg of electrolytic copper was melted in a graphite crucible having an inner diameter of 6 mm and a depth of 200 mm using a krypton-frequency induction furnace. After the surface of the melt was covered with a charcoal sheet, Zn and Sn were added. It is necessary to add CuS to adjust the s concentration and add CuO as needed to adjust the cerium concentration. After adjusting the temperature of the melt to 1200X: the melt is cast into a mold to make a casting having a width of 6 〇 1 ^ claw and a thickness of 30 mm. The ingot was processed to a thickness of 0.3 mm using the following procedure as a standard step. (Step 1) After heating at 85 Torr: 3 hours, hot calendering (hot rolling) to a thickness of 14 1327173 was 8 mm 〇 (Step 2 The rust scale on the surface of the hot rolled plate is ground and removed by a grindstone (Step 3) cold calendering (primary calendering) to a plate thickness of 1.5 mm (Step 4) as recrystallization annealing (intermediate annealing), The film was heated at 4 ° C for 30 minutes in the atmosphere to adjust the grain size to about 3 μm. (Step 5) Sour pickling with 10% by mass of sulfuric acid-1% by mass of hydrogen peroxide solution, and #1200 Mechanical grinding of abrasive paper to remove surface oxidation generated by annealing (Step 6) Calendering to a thickness of 0.43 mm by cold rolling (intermediate calendering) at 71% (Step 7) as recrystallization annealing (final annealing), heating at 4 ° C for 30 minutes in the atmosphere. The grain size is adjusted to about 3 μm. (Step 8) Acid washing with 1% by mass of sulfuric acid_1% by mass of hydrogen peroxide solution and mechanical grinding with #12〇〇 abrasive paper are sequentially performed to remove The surface oxide film formed by annealing is (step 9) calendered to 0.3 mm by a cold rolling (final calendering) of 3% by weight. The following evaluation was performed on the prepared sample. The measurement of the inclusions will be parallel to the cross section in the rolling direction and the thickness direction, and machined into a mirror surface by mechanical polishing. The optical microscope is used to observe at a magnification of 400 times, and the length (width of the rolling direction) is 5 or more. The number of objects. Inclusions composed of particles extending in the direction of rolling (B $ depleted matter), 15 1327173 • Particle groups distributed at intervals of 1 to below are regarded as one inclusion. The measurement of the inclusions is performed on the area of the 100th position, and the number of the confirmed inclusions is converted into the number per 1 mm2. Grain shape

Observe the structure of the section parallel to the calendering surface for the completion of the intermediate annealing, the completion of the fear, and the final annealing of the B and the final calendering. After the calendered surface was processed into a mirror surface by mechanical polishing and electrolytic polishing, the crystal grain boundaries were observed by etching, and a photograph of the structure was taken. The money engraving liquid is an aqueous solution in which ammonia water and hydrogen peroxide water are mixed, and the photographing of the photograph is suitably carried out using an optical microscope and a scanning electron microscope. On the other hand, when the crystal grain is pinched and it is difficult to discriminate the crystal grain boundary by chemical silver etching, the mirror sample which is subjected to electrolytic polishing is used, and the orientation image is taken by EBSP (Electr〇nρ_Γη, electron backscatter pattern) method. This image was used to measure the grain shape. The above-mentioned tissue image ' is drawn in a direction orthogonal to the rolling direction, and the number of crystal grains cut by the straight line is obtained. The value of the length of the straight line divided by the number of the crystal grains is determined to be the same, a straight line is drawn in a direction parallel to the rolling direction, the number of crystal grains cut by the straight line is obtained, and the length of the straight line is divided by the crystal. The value of the number of grains is set to b. For the sample which completed the intermediate annealing and completed the final annealing, the value of (a + b) /2 was determined and regarded as the grain size of the finished annealing. When the final calendered sample is completed, the value of b/a is obtained. Diffraction Ding Tang uses RINT2500 (science) to use the X-ray diffraction device to make 16 1327173 - use Co ball to measure the integrated strength of (200) and (22) faces on the rolling surface of the sample. . Further, the same measurement was carried out on the copper powder sample of 325 mesh. Conductivity was measured by a 4-terminal method in accordance with JIS Η 0505. Tensile strength A JIS 13B test piece was produced using a press machine so that the stretching direction was parallel to the rolling direction. The test piece was subjected to a tensile test according to JIS - Ζ 2241 to determine the tensile strength. For bending workability, a slender specimen of width l〇mm is used, based on jIS ζ 2248, in Good Way (direction in which the bending axis is orthogonal to the rolling direction, hereinafter referred to as "orthogonal direction") and Bad Way (bending axis) The direction parallel to the rolling direction, hereinafter referred to as "parallel direction", was subjected to a 180 degree close bending test. For the bent sample, the surface and the cross section of the bent portion were observed for the presence or absence of cracks and the degree of surface wrinkles. • When cracks were not generated and the surface wrinkles were slight, it was evaluated as 〇. Although no crack was generated, the surface was found to be Δ' when the surface was severely broken, and X was evaluated when the crack occurred. Further, in conjunction with the 180-degree adhesion bending test, a 90-degree W bending test of R = 0.24 mm (R/t = 0.8) was also performed according to JIS H 311, and all the inventive examples and comparative alloys described later were Both the orthogonal direction and the parallel direction were evaluated. (Example 1) The influence of the concentration of Sn and Zn on the electrical conductivity and the tensile strength was explained. The sample having the Sn and Zn concentrations of Table 1 and a thickness of 17 1327173 degrees of 0.3 mm was prepared by the above standard procedure. The S concentration of the samples was adjusted to the range of i〇~u mass ppm, and the germanium concentration was adjusted to 2 〇 ~ 3 〇 mass ppm range. Further, the number of inclusions having a length of 5 〇 Mm or more is 〇". Further, a is about 3 μm, b/a is JH, 丄(200)/丄〇(200) is in the range of 0·4 to 0.6, and I /τ (220〆1〇(22.) is 4.0 to 4.5). In addition, for any alloy, the results of the 180 degree close bending test in the orthogonal direction and the tenth direction are all 〇. ~ & π bow

18 1327173 [Table 1]

ΧΤΛ Zn Sn [%Sn] + 0.16[%Zn] Other added elements Conductivity Tensile strength lNU. (% by mass) (% by mass) (% by mass) (%IACS) (MPa) Issue 1 8.1 0.12 1.42 — 43.6 445 Ming 2 8.0 0.29 1.57 — 41.0 472 Example 3 8.1 0.46 1.76 — 38.6 476 4 8.0 0.67 1.95 — 35.0 479 5 2.7 0.29 0.72 — 58.3 417 6 3.5 0.30 0.86 — 54.9 430 7 4.8 0.30 1.07 — 50.1 442 8 6.2 0.30 1.29 — 46.0 463 9 8.6 0.31 1.69 — 39.0 474 10 10.4 0.30 1.96 — 35.5 480 11 2.2 0.69 1.04 — 50.6 461 12 3.1 0.19 0.69 — 60.2 420 13 3.3 0.54 1.07 — 49.4 443 14 3.8 0.95 1.56 — 40.4 492 15 4.0 0.42 1.06 — 50.0 450 16 5.0 0.79 1.59 — 40.8 487 17 5.1 0.20 1.02 — 51.2 439 18 5.5 0.55 1.43 — 44.3 473 19 5.9 0.14 1.08 — 49.6 428 20 6.0 0.68 1.64 — 40.2 480 21 6.3 0.92 1.93 — 36.0 494 22 6.9 0.25 1.35 — 45.2 468 23 7.0 0.65 1.77 — 39.1 479 24 7.2 0.43 1.58 — 41.2 475 25 9.0 0.51 1.95 — 35.5 491 26 9.1 0.18 1.64 — 40.9 462 27 10.2 0.13 1.76 — 38.4 472 28 11.5 0.12 1.96 — 35.3 464 29 4.7 0.18 0.93 — 51.7 437 30 2.7 0.17 0.60 — 59.4 417 31 2.5 0.16 0.56 — 61.4 414 32 8.0 0.30 1.58 0.25Ag 40.7 483 33 7.9 0.31 1.57 0.18Ni 37.4 496 34 8.0 0.29 1.57 0.05ΤΪ 38.1 510 19 1327173

35 5.0 0.20 1.00 0.03P 45.6 452 36 5.0 0.19 0.99 0.08Mg 48.0 464 37 0.20 1.02 0.1 OFe 46.2 450 38 5.1 0.20 1.02 0.20Mn 43.2 452 _39 4.9 0.19 0.97 0.05Zr, 0.1 Cr 49.2 471 40 8.1 0.32 1.62 0.05Be, 0.02 C〇39.6 503 41 7.8 0.30 1.55 0.08A1 38.4 491 Ratio 42 8.0 0.03 1.31 — 45.8 398 Compared with 43 7.9 0.80 2.06 — 33.3 482 Example 44 U 0.22 0.49 — 62.5 407 45 122 0.30 2.25 — 31.4 486 Conductivity and tensile strength The measurement data is shown in Table 1. Inventive examples No. 1 to 41 in which the concentrations of Sn and Zn were adjusted to the following ranges were obtained, and the target had a conductivity of 35% IACS or more and a tensile strength of 4 i 〇 MPa or more. [%Zn]=2~12, [%Sn]=0.1 〜1.0 0.5^ 2.0 T= [%Sn]+ 0.16[%Zn] No.1~4 of the invention example, Νο·42,43 of the comparative example The Zn was determined to be 8%, and the concentration of Sn was changed. If Sn is increased, the electrical conductivity is lowered and the tensile strength is increased. Sn is less than 0.1% of No. 42 and has a tensile strength of less than 410 MPa. At No. 43, T exceeded 2 and the conductivity was less than 35% IACS. In No. 2, 5 to 10 of the invention examples and No. 45 of the comparative example, Sn was changed to 0.3%, and the Zn concentration was changed. If Zn is increased, the electrical conductivity is lowered and the tensile strength is increased. In No. 45 where Zn exceeds 12%, T exceeds 2 and the conductivity is lower than 35% IACS. The No. 44' tensile strength of T less than 0.5 is less than 410 MPa. Fig. 2 shows the relationship between τ and conductivity using data of Inventive Examples 1 to 31 and Comparative Examples 42 to 45 in which elements other than Sn and Zn were not added. 20 1327173 Knowing that τ has a close relationship with conductivity. (Example 2) The influence of the S, the concentration of bismuth and the number of inclusions on the bending workability was explained. The S and 〇 different cu~2n-Sn alloy ingots shown in Table 2 were produced by the above method. Among them, in the case of producing an ingot having an s concentration of 5 ppm or less, sodium carbonate is added to carry out a desalination treatment. Further, in the case of producing an ingot having a crucible concentration of 5 ppm or less, the raw material is melted in an argon gas stream. The standard steps are to process the castings to a thickness of Q3 mm. The a of the samples is about 3 μm, and the b/a is about 1.4, and I 〆 τ Α ( (200 > / 1 〇 (2 〇〇) is in the range of 0.4 to 0.6 '1 (22. 〆 ^ 0 (22. ) is in the range of 4.0 to 4.5.

twenty one

180 degree tight bending parallel direction ° 〇〇〇〇〇〇〇〇〇〇〇〇〇〇XI XI XI orthogonal direction 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇X] XI tensile strength (MPa) 472 473 474 472 — 1 470 I 471 472 470 477 472 ν〇1 418 469 433 496 469 472 475 Conductivity (%IACS) 41.0 41.0 41.3 1 41.0 I 41.2 1 41.0 1 41.0 41.2 41.0 51.0 1 60.4 39.5 54.7 35.5 41.0 41.5 41.1 Number of inclusions (pieces/mm2) 0.00 0.00 0.00 0.15 0.21 0.00 0.00 0.00 0.09 0.26 0.00 0.46 0.00 0.02 0.00 a 3 1 〇 (mass ppm) 00 CN Ο CN 〇\ CA cs inch CN CN CN oo 卜o ro CO (mass ppm) 〇\ Vi 00 CN m inch CN ν〇rH CN 00 CN CN VO [%Sn]+0.16[% Zn] 1.58 1.56 1.60 1.57 1.58 1.56 1.57 1.55 1.57 1.60 1.02 0.67 1.72 0.86 1.93 1.56 1.58 1.57 eg (% by mass) 0.30 0.28 0.30 0.29 0.30 | 0.30 | 0.29 0.30 0.29 0.30 0.20 0.19 1 012 0.30 0.94 0.28 0.30 0.29 N (% by mass) 1_ 〇00 o 00 oo o 00 o 00 ON o 00 00 Ο οό οό uS Ο ro 10.0 in rn CN vd o oo o oo Ο 〇6 CN cn V 〇 oo N 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 The number is 〇5/mm2 〇The samples are tightly bent at 180 degrees, and no cracks are formed in the orthogonal direction and the parallel direction, and the surface wrinkles are small. In the examples of the invention, No. 1 to 5, and No. 16, 17 of the comparative example are 8% Zn - 〇.3% of the Sn alloy, and the amount is determined to be 25 to 30 ppm by mass, and the s-moisture is changed. No. 16 and 17 in which S exceeds 30 mass ppm, and the number of inclusions exceeds 个 5 / mm 2 ' and cracks are formed at 180 degrees in close contact with each other. In the examples of the invention, No. 3, 6 to 10, and No. 18 of the comparative example were 8% Zn - 3%.3% Sn alloy and S was set to 12 to 15 ppm by mass, and the yttrium concentration was changed. When No. 18 of more than 50 mass ppm, the number of inclusions exceeds 〇" / mm2, and the crack is caused by tight bending at 180 degrees. (Example 3) Description of crystal grain shape 'Crystal orientation of rolling surface, influence of manufacturing method on tensile strength and bending workability 1 The above method was used to manufacture Cu-Zn-Sn* gold casting of Table 3, and processed to a thickness of 〇3 with. In this process, the thickness is changed relative to the standard step, which is changed to the calendering (step 3) and the intermediate extension (step 6). Anneal, 纟0 day annealing (step 4) and the most line time 疋 is 30 minutes, and the heating temperature is changed. 23 1327173

180 degree close-fitting back curve x| X| <] 〇〇〇〇xl X < 〇〇〇〇0 〇〇〇〇〇〇〇〇〇〇〇XI <] 〇〇〇 〇〇xl 〇〇〇〇<〇〇〇〇<1 tensile strength (MPa) 384 inch m 3 CN 00 »r> g Ό 3 <s 00 (S Tf v〇 inch 〇 \ <N «Ο Ri inch ro Ό JO ss inch inch V) w CN TO s inch s inch conductivity (% IACS) 40.8 40.9 40.5 j 40.6 40.7 40.7 40.6 40.4 50.2 50.3 49.9 50.1 49.8 49.5 48.7 45.3 45.0 45.0 45.0 44.9 ! 40.7 40.6 40.4 40.6 40.6 Plane orientation, 1/10 m 2.43 | 3.52 4.25 4.56 j 4.75 4.96 3.71 3.91 4.15 4.28 4.40 4.46 4.59 4.65 4.56 4.35 4.27 4.15 4.63 4.49 4.31 4.23 4.05 ο 0.92 0.78 0.62 :0.44 1_- . -_ 0.36 0.31 0.26 0.22 0.49 0.53 0.54 0.54 0.55 0.53 0.51 1 0.27 0.55 0.91 3 i 0.22 0.55 0.82 a Grain shape *5 1.17 <N 1.32 ON vq 2.00 2.33 \2M 茛<N 1.44 1.42 1.44 1.44 1.47 1.45 >〇v) 1.42 1.42 1.45 Vn ^ 1 >w rn r<i inch<N 'do 〆〇00 ΓΟ wS 〇VO — r4 pv〇 inch * inch · — «Ο · <N inch · c^i 卜c<i rN — inch PO « I Sw> 〇〇c0 00 <N (N r〇rn o ΓΛ o CO 1 ro fO (N rS Vq a ΓΊ p〇o ΓΟ ro OS fN rS v〇<N VO <N ON «Ν CO 〇 final calendering degree (%) g 18.9 25.0 40.0 50.0 a 3 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 30.2 Plate thickness (mm) r<i cJ Γ<·> 〇dddd 〇PO dddmd ΡΛ dddoc〇domdmddr*jdo ΡΛ dm 〇CO d final annealing 柽(um) o On CO 〇s CN o Ro o rn ON o rn 3 00 vq inch · ΓΛ VO ON «Ν fO ΓΛ oo <N oo rS 00 CN o CO ro <N temperature 〇 〇 inch 〇o 〇 inch 〇o 〇 inch inch O s Rt •n cs 〇s ΓΛ o 〇叶〇 inch o 〇 inch O 〇叶 o inch o inch 〇 inch 〇 intermediate calendering degree (%) 76.7 75.3 1 73.3 71.3 60.0 53.3 46.7 36.7 71.3 71.3 71.3 71.3 71.3 71.3 71.3 3 38.6 71.3 82.8 71.3 71.3 71.3 71.3 71.3 Plate thickness (mm 0.35 0.37 0.40 !〇.5〇0.60 0.70 0.80 0.95 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 Intermediate annealed granules (μηι) o rn OS CN <N rn o co o cs CO <N PO o CO cn (N ri ίΝ ΓΛ CO o rn o ro o OS CN OS CN 寸CO c<i 13.8 v〇00 On tN 00 Temperature (°C) 〇inch〇rr 〇o 〇Tf o 〇 inch o inch 〇 〇 inch o inch 〇 inch 〇〇 inch inch inch inch inch inch inch o o inch inch inch gg CO plain rolled plate thickness (mm) >〇»〇in «η ir> 〇o o »〇fN o U"i in u-ϊ in [%Sn] + 0.16 [%Zn ] s 1.62 v〇CO V〇1.62 <N v〇1.62 1.64 1.09 1.10 m vq 1.08 g 1.37 1.34 Ui rn «sv〇v〇sst〇vq Sn (% by mass) 0.29 S 0.28 0.29 0.28 0.28 0.28 0.29 0.28 0.29 0.30 0.30 0.29 0.30 0.30 0.29 0.25 0.24 0.25 0.23 0.24 0,20 0.20 0.19 0.20 0.19 Zn (% by mass) 2 «λ 〇〇ΓΛ 00 00 00 m 〇6 W"> od o »τϊ 00 — o »〇ON — 〇\ 々· Ov — q 〇\ v〇〇\ v〇o 卜v〇〇\ oo 00 od Os oo o 〇\ σί i I comparative example | I invention example | invention example | invention example | | 1 invention example comparative example | comparative example | I invention example 1 | invention example | 1 invention example | invention example comparison example 1 comparative example|comparative example| | invention example invention example invention example Inventive Example Inventive Example Comparative Example Inch v 〇 00 〇 \ o < sv 〇 00 α \ < N 1327173 Table No. 1 to 8 ' is changed by changing the thickness of the middle to change The final calendering process. Further, the intermediate calendering degree of these is within the scope of the present invention. With the increase of the final calendering degree, b/a becomes larger, l(200)> 1(220)/ 1〇(220) liters, the final calendering degree is less than 15% of No.l, b/a is lower than 丨2. 丨 (2 2 0 ^ / 1. (2 2 ()) is lower than 2_0. The tensile strength of No. 1 is lower than 41 〇 MPa.

No.7 and 8 are those in which the final rolling degree exceeds 60%. At N〇 7,b

/a exceeds 2.5» in No.8, the deformation of the grain is large and it is impossible to measure ^ and b/a, and ϊ(22〇〆10(220> exceeds 5.0. 180 degree tight bending, in the parallel direction of N〇7 Cracks are generated and cracks are generated in the orthogonal direction and the parallel direction of No. 8. No. 9 to 15 in Table 3 are used to change the grain size of the final annealing by changing the final annealing temperature. As the grain size of the final annealing becomes larger, a also becomes larger. The grain size of the final annealing exceeds 10 μm, N〇9, a exceeds ΙΟμιη. The tensile strength of N〇.9 is less than 410 MPa, and Large-area surface wrinkles are produced in 18-degree tightness bending. On the other hand, the final annealing particle size is adjusted to 7.8 μm and a is 7 3 Ν〇1〇, 18 密 密 脊 脊 之 surface Wrinkles Although Xiao Ng.u ~ 13 is slightly larger, but practically no: the title is judged as grade (〇). However, in the case of paying special attention to the curved appearance, 'preferably' will complete the final annealing grain size Adjusted to 5μηη or less and a to be 5gm or less. ι凡成The grain size of the final annealing is less than Νο·14, a is lower than km. In N〇·14, in parallel Cracking to produce the turtle 251327173 180 ° adhesion bending.

No. 15 is the case where the final silver order is completed, and the non-recrystallized portion (calendered structure) remains in the large time, and the measurement of a and b/a is not possible. Νο·15, in the 18-inch production tight bend, cracks occur in the orthogonal direction, flat and 1 仃 direction.

Table 3 ο ο _ 16 2 0, ζίίι I is to change the intermediate calendering degree by changing the thickness of the finished calendering.

As the intermediate calendering process increases, I (200) / 1 〇 (2 〇〇) rises, while Ιί22 〇, / I 〇 (22G) decreases slightly. The intermediate calendering degree is less than 15% & Μ, which is lower than 〇·2. Yu Yu. • 16, a 180 degree parallel in the parallel direction produces a severe surface sensitive finger in the f curve. The intermediate calendering degree exceeds 9〇% of the chaos 20, and 1 (200/1〇(2〇〇) exceeds 1.0. In No.20, the positive $太a ★, „18-degree close-fitting bending in the direction of the father Severe surface wrinkles are produced. Table 3 - - , you change the intermediate annealing temperature to change the grain size of the intermediate annealing. The grain size changes with the completion of the intermediate annealing = 1, (2). ) / 1. _ rise, * 1 (22. 〆 '2.) slightly lower. The grain size of the intermediate annealing is over 1〇μπΐ2 N〇21, which is (yes) / less than 0.2. 21, in the parallel direction of the 18-degree tightness, the bending causes severe surface wrinkles. Ν〇·25, the intermediate annealing has no recrystallized portion (calendered structure) and the average grain size cannot be adjusted to 1 μm In the above, ^/ 'called more than 1.0 1NO.25' in the orthogonal direction of the 18-degree close-fitting bending produces severe surface wrinkles. 26 1327173 [Simple diagram of the diagram] Figure 1, is a schematic diagram of the bending test method Fig. 2 is a graph showing the relationship between T and conductivity using data of Inventive Examples 1 to 31 and Comparative Examples 42 to 45 in which elements other than Sn and Zn were not added. [Main component symbol description] None

27

Claims (1)

1327173, invention test No. 880 (amended in October, 1998) ^Year (October Z曰 Amendment 1) A copper alloy for electric and electronic equipment, characterized in that it contains 2 to 12% by mass of Zn and 0.1 to 1.0% of Sn. The relationship between the mass % concentration of Sn ([% Sn]) and the mass % concentration of Zn ([% Zn]) is adjusted to the following formula, and the remainder is composed of copper and unavoidable impurities. The concentration is 30 mass ppm or less, the cerium concentration is 5 〇 mass ppm or less 'and the electrical conductivity of 35% I ACS or more and the tensile strength of 41 〇 MPa or more' can be parallel direction (the direction in which the bending axis is parallel to the rolling direction) • 180 degree close bending of the orthogonal direction (the direction in which the bending axis is orthogonal to the rolling direction); 0.5^ [% Sn]+ 0.16[%Zn]^ 2.0 and 'parallel to the metal structure of the section of the calendering surface The crystal grains constituting the metal structure have a shape stretched in the rolling direction, and the average particle diameter of the crystal grains in the direction orthogonal to the rolling direction is a, and the average particle diameter in the direction parallel to the rolling direction is b. With the following dimensions, a = 1.0~1〇·〇μιπ, b/a= 1.2~2·5 Further, the diffraction intensities of the x-rays obtained from the (200) plane and the (220) plane of the calendering surface are Ipoq and Bu 22, respectively, and the (2〇〇) plane and the (22〇) plane of the copper powder are obtained. When the X-ray diffraction intensities are 1〇(2(9)) and 1〇(22〇), respectively, 〇·2^Ι(2〇〇)/Ι0(200)^ ι·〇2.0^ ^(220)/^ 10 (220) = 5.0 ο 2. The copper alloy for electric and electronic equipment according to claim 1, which contains Ni, Mg, Fe, Ρ, 28 1327173 I _, Co, Be in a total range of 0.005 to 0_5% by mass. And one or more elements of Ti, Cr, Zr, A1, and Ag. 3. The copper-clad # for electrical and electronic equipment of claim 1 or 2, wherein the cross section parallel to the rolling direction and the thickness direction, The number of inclusions whose length exceeds 1 is 0_5/mm2 or less. 4. For the purpose of the patent range, the 15th and 2nd items of the electrical and electronic equipment are copper. Gold 'where' a=1.0 〜5 .Ομπι. 5. A method for producing a copper alloy for an electric and electronic device, which is used for the manufacture of a steel alloy for electric and electronic equipment according to items i to 4 of the patent application, characterized in that the following steps are carried out in sequence. : Α·intermediate recrystallization annealing, fine grain size, war 1 ～1 Ομιη; Β·degree of processing 35~90% of intermediate cold rolling; C. final recrystallization annealing 'grain particle size finishing 1 battle 1 ~ 1 Ομπι; * D · processing degree 15~60% of the final cold rolling. 6. The method for producing a copper alloy for an electric and electronic machine according to claim 5, wherein the crystal grain size of the step C is ι 5 μμι. XI. Schema: as the next page 29