TW201245471A - Co-Si-BASED COPPER ALLOY SHEET - Google Patents

Abstract

To provide a Co-Si-based copper alloy sheet which has excellent solder wettability and undergoes the formation of fewer pinholes upon being soldered. A Co-Si-based copper alloy sheet containing 0.5-3.0 mass% of Co and 0.1-1.0 mass% of Si, with the remainder being Cu and unavoidable impurities, wherein a requirement represented by the following formula is fulfilled: [60 degrees specular glossiness G in the direction parallel to the rolling direction (RD)] - [60 degrees specular glossiness G in direction transverse to rolling direction (TD)] = 90%.

Description

201245471 -» VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a C0_Si-based copper alloy sheet. [Prior Art] Co-Si copper alloy (Carson alloy) having excellent strength has been developed to miniaturize electrical and electronic equipment such as connectors. However, since the Caesar alloy is formed of precipitates from Co and Si, it is required to be solid-solved or aged at a high temperature to form a strong oxide film on the surface, which deteriorates solder wettability. Further, since the Carson alloy also has a step of performing relaxation annealing after final rolling, it causes the oxide film to further grow. Therefore, after the final heat treatment, pickling is performed to dissolve the oxide film, and a step of removing the oxide film by buff polishing (hereinafter referred to as "washing and polishing" is preferable). As a result, a copper alloy material having a surface roughness Ra of 〇 2 or less and an Rt of 2 μm or less and improved solder wettability has been developed (Patent Document 1). Further, when the above-described pickling polishing is performed, the solder wettability is reduced due to the ridge-like irregularities caused by polishing on the surface, so that pickling or degreasing treatment is performed before the finish rolling, and the solder is wetted. A copper alloy material having improved wettability (Patent Document 2). If the pickling or degreasing treatment is carried out before the finish rolling, the peak position in the degree distribution map indicating the surface unevenness component appears on the average line of the roughness curve (zero position in the degree distribution map). (Convex component), which improves solder wettability or plating properties. In the case of the technique described in Patent Document 1, even if it is in the case of the technique described in Patent Document 1, even if it is in the case of the technique described in Patent Document 1, the patent document 1 is disclosed in Japanese Laid-Open Patent Publication No. 4,131,992. The solder wettability is good, and the oxide film on the surface of the material cannot be removed cleanly. Or it is pickled and ground before the final rolling. Therefore, if foreign matter is pressed in due to rolling, a pinhole will be generated (partially unattached). Area of solder). If the number of pinholes is increased, soldering defects are likely to occur, and in particular, if a pinhole is formed in a portion where solder is formed when the Carson alloy is formed into a terminal, soldering failure may result. Further, in the case of the technique described in Patent Document 2, since the pickling or the degreasing treatment must be performed before the finish pressing, the steps become complicated and the productivity is deteriorated. Moreover, the oxide film of the CG_Si-based Carson alloy is very strong, so it is not easy to be peeled off by pickling only, and the technique described in Patent Document 2 is

Membrane, and easy to make pinholes.

Co-Si copper alloy plate β

Pickling and polishing, the polishing wheel is subjected to a sufficient number of final heat treatments to remove the oxide film on the surface of the material or by calendering, and by making the surface have a surface, the solder is excellent in wettability. And the pinhole will be reduced. , Millennium. C. ·. For the purpose of 5 达, the invention is a copper alloy plate containing LO. 0.5~3.0 mass %, s " and unavoidable impurities: and

Surface gloss factory firm straight = Yan Zhiping ^ 6 〇 〇 镜 (TD)) ) ^ 〇 〇 〇 直 直 直 镜 镜 镜 镜 镜 镜 镜 镜 镜

Preferably, the Yan Yanping A is thicker than the coarseness Ra (RD) by .G7叩. ::"The surface of the parallel direction is rough." Cloth:: is the degree of the surface unevenness of the room in the direction of the right angle; the peak position of the curve in the distribution diagram (the concave component side). The average line is preferably on the negative side, and further preferably contains 2% to 〇% by mass or less selected from the group consisting of "Μ", 2: 1, (: Γ, V, Nb, M., Zr, B, Ag, Be, Zn, According to the present invention, it is possible to obtain a Co-Si-based copper alloy which is excellent in solder flow and has less pinholes during soldering. [Embodiment] The following is a description of the "Si-based copper alloy sheet according to the embodiment of the present invention." In the present invention, the % is % unless otherwise specified. - Further, the surface roughness is as follows. Ra refers to JIS B〇6〇i (2〇〇1), and the center line average roughness of the crucible 'the so-called surface roughness Rz refers to the maximum height specified by the claw. 201245471 First, referring to FIG. 1, the present invention is The technical idea will be described. Fig. 1 shows a manufacturing step of a Co_Si-based copper alloy sheet according to an embodiment of the present invention. An example: First, 'the copper alloy plate 2 after the final heat treatment is introduced into the pickling tank 4 to pick up the pickling', and in the rolling parallel direction (RC)) and the rolling orthogonal direction (td), the oxide film is dissolved substantially uniformly to change the thickness. Therefore, the 60-degree specular gloss g(RD) in the parallel direction after pickling and the 60-degree specular gloss G(TD) in the right-angle direction are approximately the same, and the difference is {G(rd) - G ( TD) } and 〇 (refer to Figure 1 (a)). Secondly, if the copper alloy plate after pickling is polished by the polishing wheel 6, it will be attached with a scratch of the polishing trace caused by the polishing wheel. In the rolling parallel direction (RD) in the direction of rotation, the oxide film which cannot be dissolved by pickling disappears from the surface of the material due to the polishing of the surface of the material, so that the surface of the material becomes smooth and G (RD) becomes large. On the other hand, even if the surface of the material is polished in the direction of the right angle of the rolling (TD), since the surface of the material in the TD direction is formed with a scratch of the polishing trace caused by the polishing wheel, the degree of smoothness of the surface does not largely change, and G (td) has not changed much. Therefore, Break: If {G(RD) _g(td)丨>〇, and {G ( RD ) .G ( TD ) } $ 9G%, polishing and polishing will sufficiently remove the oxide film, and the solder wettability will be improved. The pinholes during welding will be reduced. Although the upper limit of {G( RD)TD) Bu I I & ^ u W is not specified, it is more practical than 4〇〇%. * Furthermore, 60 degrees The specular gloss reflects the surface state of the material in a specific area. On the other hand, the surface roughness (Ra sheep) reflects the surface state of the material on a specific line. Therefore, it is considered that: 60 钟 clock face 氺., Λ Λ 度 镜 镜 先 先 先 先 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Further, the polishing wheel 6 has a cylindrical shape, and abrasive grains adhere to the surface thereof. Further, the polishing wheel 6 is rotated in the direction of the through-plate of the copper alloy plate 2 (from the left to the right) to cut the abrasive grains of the polishing wheel 6 over the surface of the copper alloy plate 2. Therefore, the degree of removal of the oxide film by polishing and polishing can be adjusted by using the particle size (particle size) of the abrasive grains, the number of passes of the copper alloy plate 2, the plate speed (linear velocity), the number of rotations of the polishing wheel 6, and the like. Further, it is preferable that the surface roughness Ra (RD) in the rolling parallel direction is 〇.〇7 μηι or less. When Ra ( RD ) is 〇 ( 7 (4) or less, there is a case where the soldering time C zero cross time becomes small. In the present invention, the peak position in the power distribution map of the surface unevenness component in the direction perpendicular to the rolling direction may be specified. Here, the degree distribution map of the surface unevenness component is the same as that described in Patent Document 2, and the horizontal axis is the height from the average line for the roughness curve, and the vertical axis is plotted as the frequency (measurement data number). Figure. Further, in the present invention, the horizontal axis is set at intervals of 0.05 μm from the average line of the roughness curve, and the number of measured data per s of the interval is totaled as frequency and plotted. . Furthermore, the "average line for the coarseness curve" is defined by JIS_B〇6〇1. The degree distribution map is specifically produced as follows. (1) First, the direction perpendicular to the rolling direction of the sample is measured, and the "height from the average line for the roughness curve" is measured, that is, the height from the average line for the roughness curve can be obtained at each surface position. The data (hereinafter referred to as "measurement data" is appropriate)" Therefore, the peak position and the like can be obtained from the obtained measurement data, and the data of the measurement data of 201245471 can be calculated to calculate Ra and RZQ (2) from "roughness". The height of the curve is separated by a height of μ5 μηι. (3) The number of measurements (degrees) is counted at intervals of 0. 〇 5 μηι. Further, the measurement data was measured with a standard length of 1.25 mm, a cutoff value of 25 mm (according to JIS_B0601), and a scanning speed of 〇丨mm/sec. The surface roughness measuring machine (Surfcorder SE3400) manufactured by Kosaka Research Co., Ltd. was used for the measurement, and the measurement length was K25 mm, and the number of measurement data was 75 00. The specific measurement method of the above-described peak position is also the same as that described in Patent Document 2, and in the obtained measurement data, the component having a height greater than 0 from the "average line for roughness curve" is set to the upper (positive) component. The degree distribution is plotted by classifying less than 〇 as the lower (negative) component. When the horizontal axis is taken as the height from the "average line for the roughness curve" (μιη and the number of measurement data totaled at 0.05 μm is used as the frequency and redrawn as the vertical axis), FIG. 2 and FIG. 3 can be obtained. In Fig. 2 and the circle 3', if the height from the "average line for the roughness curve" from the line to the horizontal axis is Ομιη, the peak position of the frequency can be determined as concave. Component (negative side), convex component (positive side), (or ytterbium). Here, the above-mentioned "peak position" is determined as follows. First, the average line from the frequency/self-roughness curve is used. In the height map (see Fig. 2 and Fig. 3), the frequency with the highest value is P1, and the frequency of the next highest value is P2. Moreover, (1) the peak position is the concave component (negative side) Refers to the case where both pi and P2 are on the negative side, or Ρ2/ρι<99%& is on the negative side. (2) The so-called peak position is convex component (positive side) system 8 201245471 ==. In the case of positive r, ... (for the removal of 2, the location of the bee bee is 0 means P2 (four) 99% ... The mean =::2 is located on the negative side, ... outside the case of the % positive side.) The average line from the roughness curve refers to the average line used for the crude sugar curve. The % is the line of Gp. The positive spot "is based on the measurement of the results of the three times, the peak position is dispersed as convex: Λ The peak in the second measurement is in the upper (positive) component, then it is regarded as the convex component side. The frequency is based on / described in the example The actual measurement data of 4 is plotted on the vertical axis '::/. The k-axis is a re-rendered height (Mm) from the average line of the roughness curve. Further, Fig. 3 is based on the actual measurement of the following Example 18. The data is plotted on the vertical frequency (./〇) and the horizontal axis is the height (μηι) from the average line of the rough shuttle curve. In the case of Fig. 3, the degree distribution of the surface irregularities is known. In the case where the peak position is closer to the positive side (convex component side) than the average line of the roughness curve in the figure, it can be seen that the peak position is closer to the negative side (the concave component side) than the average line of the sharpness curve. That is, even in the present invention (for example, FIG. 2 and Embodiment 4), even the peak position On the negative side (concave component side), the wettability was also good, and the wettability was not determined by the peak position. Further, in Example 18, the peak position was made positive by changing the pickling liquid during pickling. The method for measuring the surface roughness saccharides Ra and Rz is the same as that described in Patent Document 2, and is measured by a standard length of 2525 mm, a cutoff value of 25 claws (according to 201245471 JIS-B060 1 ), a scanning speed of 〇·1 mm/sec, and a. , m ^ 〗 疋. The measurement system uses the surface roughness measuring machine (Surfcorder SE3400) manufactured by Kosaka Kenji Co., Ltd. 'The measurement length is 1.25 mm and the measured data is only 4,500 points. Further, the surface roughness Ra and Rz were measured three times and the average value thereof was taken. Next, the Co-Si-based copper alloy sheet of the present invention will be described in terms of its specifications and composition. <Composition> 0 · 1 to 1.0% by mass and the remainder contains Co: 0.5 to 3_0% by mass, Si: Part is Cu and unavoidable impurities. When the content of Co and Si is less than the above range, the precipitation strengthening of c〇2Si is insufficient, and the increase in strength cannot be achieved. On the other hand, when the content of c〇 and & exceeds the above range, the electrical conductivity is deteriorated and the hot workability is deteriorated.

The content of Co is preferably from k5 to 2.5% by mass, and more preferably from 丨2 to 2% by mass. The preferred content of Si is 〇·3~〇 7 mass. More preferably, the content is 0.4 to 0.55 mass%. The c〇/Si mass is preferably from 3 to 5 to 5.0, more preferably from 3.8 to 4.6. If the Co/Si mass ratio is in this range, C 〇 2 S i can be sufficiently precipitated. It is preferable to further contain a total of 2.0% by mass or less selected from the group consisting of Mn, Mg, Ag, p, B, Zr, Fe, Ni, Cr, v, Nb, M〇, Be, Zn.

One or two or more of the group consisting of Sn and a bismuth alloy. When the total amount of the above elements exceeds 2.0% by mass, the following effects are saturated and the productivity is deteriorated. However, when the total amount of the above elements is less than 0.001% by mass, the effect is small. Therefore, the total amount of the above elements is preferably 0.001 to 2.0% by mass, more preferably 〇·01 to 2. 〇% by mass, The most important position is 〇.〇4~2.0% by mass. 10 201245471 Here, by adding a small amount of Mn, Mg, Ag, and P, the product characteristics such as strength and stress relaxation characteristics are improved without impairing the electrical conductivity. These elements exert the above effects mainly by solid solution toward the mother phase, but further exert an effect by being contained in the second phase particles. By adding B, Zr and Fe, it is also possible to improve the properties of the product such as strength, electrical conductivity, stress, stress, and properties. These elements exert the above effects mainly by solid-cooling toward the mother phase, but further exert the effect by being contained in the second phase particles or by forming the first phase particles of a new composition.

Ni, Cr, v, Nb, M〇, Be, Zn, Sn, and the adhesive alloy will be mutually exclusive, complementing ''and not only for strength, electrical conductivity, but also for stress relief and special bending. Or, the manufacturability which improves the hot workability is improved by the miniaturization of an ingot structure. Further, elements not specifically described in the specification may be added to the range which does not adversely affect the characteristics of the alloy of the present invention. Next, an example of a method for producing a Co-based copper alloy sheet according to the present invention will be described. First, an ingot composed of copper and a necessary alloying element and further containing an unavoidable impurity is hot-rolled, and then subjected to surface-cutting and cold rolling, and after solution treatment, aging treatment is performed to precipitate. It is owed to a specific thickness by final cooling and extension, and further relaxation annealing is carried out as needed, followed by pickling and immediate polishing. The solution treatment can be selected, for example, in the range below the war. Also, the aging treatment can be, for example, gamma. C ~ (four). c is carried out for 1 to 2 hours. Moreover, the final calendering degree is 5~5Q%, and (4) to 30%. The wire diameter of the alloy material of the present invention is not (4) 201245471 to 20 μιη or less. The particle size of the precipitates was 5 nm to 10 μηι » [Examples] The ingots of the composition shown in Table 1 were cast and heat-rolled at 960 ° C to a thickness of 10 mm to oxidize the surface. After the skin is subjected to cold rolling, it is subjected to a solution treatment at 700 ° C or higher and 10 ° C or lower, and finally subjected to an aging treatment at 400 ° C to 65 ° C for 1 to 20 hours. Secondly, the processing rate is 5% to 40%. /. The film was finished to a specific thickness by final cold rolling, and further subjected to a relaxation annealing at 0.05 to 3 hours at 300 to 600 ° C, and finally subjected to pickling under the conditions shown in Table i and immediately subjected to polishing. Further, the pickling liquid used for pickling before polishing is an aqueous solution of dilute sulfuric acid, hydrochloric acid or dilute nitric acid having a concentration of 2 〇 to 3 〇 mass% and pH== i or less, and the pickling time of the pickling is set to 60~1 80 seconds. The polishing wheel used for the buffing is made of alumina-made abrasive grains, and the nylon non-woven fabric contains alumina. Further, a polishing wheel which changes the polishing roughness (particle size of the abrasive grains), respectively, is used. The particle size of the abrasive particles indicates the number of mesh per inch of the abrasive particles and is specified by JIS R6001. For example, if the particle size is 1 Å, the average particle diameter of the abrasive grains is 18 to 14, 5 μη. Further, in Example 18, the same manner as in the other examples was carried out except that an aqueous solution of nitric acid having a concentration of 4 Å to 5% by weight and ρ Η = 1 or less was used as pickling by pickling polishing. Each of the samples thus transmitted was evaluated for each characteristic. (1) Ra and Rz According to JIS-B060 1 (2〇〇〖year), the center line average roughness and the maximum height RZ° are measured. The parallel direction (RD) and the right angle (TD) are measured. . In the measurement, the standard length was set to 1.25 12 201245471 mm, the cutoff value was 0.25 mm (according to JIS above), the scanning speed was 〇 mm/sec, and the surface roughness measuring machine (Surfcorder 5E3400) manufactured by Kosaka Research Co., Ltd. was used. The measurement length was 丨.25 mm and the number of measurement data was set to 7500 points. (2) Degree distribution map The measurement data of the direction perpendicular to the rolling direction obtained by C 1 ) is classified into the composition of the upper (positive) component and the lower (negative) component from the "average line for the roughness curve" in the measurement data. 'Draw the degree distribution from the height from the average line of the roughness curve with a scale of 0.05 μm. According to the measurement data, the vertical axis is the frequency (%), and the horizontal axis is the height from the average line of the roughness curve (μη〇 is redrawn, and FIG. 2 and FIG. 3 are obtained. In FIG. 2 and FIG. 3, if On the horizontal axis of the horizontal axis from the average line from the roughness curve, the peak of the frequency can be determined as the concave component (negative side) or convex component (positive side), (or 〇) (3) Gloss 60 degree specular gloss is used in accordance with JIS Z8741 gloss meter (manufactured by Sakamoto Electric Co., Ltd., trade name "PG_丨M"), in the rolling parallel direction RD, and the rolling orthogonal direction TD The measurement was performed at an incident angle of 6 。. Fig. 2 is a comparison of the actual measurement data of Example 4, with the vertical axis as the frequency (%) and the horizontal axis as the height (pm) from the average line of the roughness curve. Fig. 3 shows the actual measurement data of the following Example 18, with the vertical axis as the frequency (%) and the horizontal axis as the height (μπι) from the average line of the roughness curve. Chart drawn. 13 201245471 (3) Solder characteristics (3-1) Number of pinholes The number of pinholes, Refers to the number of holes that can be observed on the substrate (copper alloy) without wetting the solder. If the number of pinholes is increased, it is easy to cause poor soldering. The number of pinholes is tested in 10% by mass aqueous solution of dilute sulfuric acid. After washing a 1 mm wide sample, it was immersed in a solder bath with a dipping depth of 12 mm, an impregnation speed of 25 mm/s, and a text collapse time of 10 sec. The number of the pinholes of the base is observed. The number of pinholes is preferably 5 or less. The solder test is carried out in accordance with JIS_C60068_2_54. The composition of the solder bath is 60 wt% of tin, 40 wt0/., and then added in an appropriate amount. Flux

235 ° C ± 3 ° C. (3-2) soldering time (T2 value)

The following is a good solder wettability.

沅 throw no grinder. For example, in Example 9, the pickling is performed before the fine dust is applied. 14 201245471 Grinding, and further, pickling and polishing are performed after the finish pressing. The pickling liquid used for pickling in the pickling polishing slurry before the finish press is the same as the pickling liquid used for the pickling and polishing after the above-mentioned fine rolling. Method A: Polishing and grinding times 1 time, plate speed 40 m/min, polishing roughness (abrasive grain) 1000 grain size, polishing wheel rotation number 500 rpm B method: polishing grinding times 3 times, plate speed 1 〇 m/min Polishing roughness (abrasive grain) 2000 grain size, polishing wheel rotation number 丨400 rpm Further, for a part of the sample, only the acid pickling was performed by dipping in a 10% sulfuric acid aqueous solution for 30 seconds before the finish rolling. Further, for a part of the sample 'before the finish rolling, only the degreasing was performed by dipping it in hexane for 3 () seconds. Further, the other samples were not subjected to any treatment before the finish rolling. 15 201245471 [1<] @5 Number of rotations (/min) 1400 1400 1400 1400 1400 1400 1400 1400 1400 1400 1400 1400 1200 1400 1400 1400 j 1400 1400 1500 Spiral rough seam (grain size) 2000 2000 2000 2000 2000 2000 2000 4000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 4000 /-N _ ·| South Street | 〇ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ΓΛ m CM ΓΟ rr» mv 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇man made step pickling 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 Relaxation annealing 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇Η ^ noun) 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇Η r - 3⁄4 ^ 1 1 • • II • 1 Α method 酸 method only pickling only defatted II 1 I 1 1 t composition (wt%) other components 1 1 1 i 1 1 I 1 I 1 I 1 I Μ η : 0.1, Fe : 0.2, Mg: 0.05, Ni: 1.2 Cr : 0·1, V : 0.2, Nb : 0 ·1, Μο : 0.1, Zr : 0.1 Β : 0.05, Ag : 0.1, Ζη : 0.5, Sn : 0.4 sd α- d 俤d < υ CQ 1 1 Λ Λ ΓΛ (N Ο Ο d Ο Ο Ο Ο Ο实施 Ο Ο Ο Ο Ο Ο ο ο 〇 〇 ο ο Ο 〇 〇 沄 沄 Ο — — 沄 沄 * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 18 Example 19 201245471 Polishing and polishing t Λ-t- tfc Jv/ 1 character-human double (/min) 1400 1400 1400 1 1400 1400 1400 1400 1400 1400 200 〇1 1 500 1 〇vn 1 〇500 1 JXj· «I·* . V*-* fir like 7〇租梅/义(particle size) 2000 2000 2000 1 4000 4000 4000 500 500 500 2000 2000 1 1 2000 1 2000 1 2000 1000 1 •^low also/夂(m/min) % 〇〇 1 〇〇»·* 〇〇〇〇〇〇〇1 1 1 S 〇1 1 Pass times m 1 - <Ν — CN ΓΊ mm — 1 1-1 — 1 Polishing 〇〇〇 1 〇〇 〇〇 〇〇〇1 1 〇1 〇1 〇〇1 Process steps Pickling 〇〇〇1 〇〇〇〇〇〇〇〇〇1 〇1 〇1 〇〇1 Relaxation annealing 〇〇〇1 〇〇〇〇〇 〇〇〇〇1 〇1 〇1 〇〇1 Processing calender 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇W shouting 3-3⁄4 1 1 1 1 1 1 1 1 1 1 1 1 1 ί A method A method only degrease only degrease only pickling only pickling 1 I composition (Wt ° / o). Spider 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.40 | 0.40 1 1 0.40 I 1 0.40 I | 0.40 I | 0.40 I | 0.40 I | 0.40 II 0.40 II 0.40 I 1 0.40 I 1 0.40 I 1 0.40 I i 0.40 1 0.40 1 1 0.40 I 0.40 0.40 0.40 0.40 0.40 〇丨J ° | 1.50 I 1 1.50 I «μ· 1.50 1.50 No. Comparative Example 1; Comparison 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 | Comparative Example 7 j Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example i4 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 | Comparative Example 19 | Comparative Example 20 Comparative Example 21 201245471 [Table 3]

No. Degree distribution curve Peak wave position Ra (μΓη) Rz (μιτι) Gloss G (60°) Soldering-characteristics RD TD RD TD RD TD G (RD) -G (TD) Pinhole number Dip soldering time (sec Example 1 - 0.05 0.08 0.42 0.6 299 191 108 0 1.61 Example 2 - 0.06 0.08 0.44 0.68 288 193 95 0 1.73 Example 3 - 0.05 0.08 0.43 0.65 288 192 96 0 1.65 Example 4 - 0.06 0.08 0.43 0.67 288 190 98 0 1.73 Example 5 - 0.05 0.08 0.44 0.66 293 192 101 0 1.62 Example 6 - 0.06 0.08 0.43 0.68 288 192 96 0 1.81 Example 7 - 0.06 0.08 0.54 0.71 288 193 95 4 1.87 Example 8 - 0.04 0.06 0.35 0.53 387 288 99 0 1.59 Example 9 - 0.06 0.08 0.42 0.68 288 189 99 1.72 Example 10 - 0.05 0.08 0.43 0.68 297 190 107 0 1.65 Example 11 - 0.06 0.08 0.42 0.68 287 190 97 1.82 Example 12 - 0.06 0,08 0.43 0.68 288 193 95 1.73 Example 13 - 0.08 0.10 0.52 0.68 274 174 100 4 1.87 Example 14 - 0.06 0.08 0.42 0.66 288 186 102 0 1.70 Example 15 - 0.05 0.08 0.43 0.67 294 188 106 0 1.61 Example 16 - 0.06 0.08 0.42 0.66 288 188 100 0 1.70 Example 17 - 0.06 0.09 0.43 0.67 288 179 109 0 1.71 Example 18 + 0.07 0.1 0.45 0.69 276 168 108 3 1.59 Example 19 - 0.04 0.06 0.23 0.37 384 280 104 0 1.20 Comparative Example 1 - 0.10 0.10 0.72 0.72 184 184 0 7 1.73 Comparison 2 - 0.13 0.14 0.76 0.78 180 168 12 8 1.88 Comparative Example 3 - 0.10 0.09 0.71 0.70 186 168 18 7 1.80 Comparative Example 4 - 0.31 0.28 1.54 1.74 123 134 -11 42 2.81 Comparative Example 5 - 0.14 0.15 0.82 0.83 160 153 7 13 1.88 Comparative Example 6 - 0.10 0.12 0.69 0.73 175 170 5 9 1.87 Comparative Example 7 - 0.07 0.08 0.49 0.60 275 190 85 6 1.80 Comparative Example 8 - 0.34 0.38 2.38 2.42 120 100 20 11 2.64 Comparative Example 9 - 0.35 0.38 2.45 2.42 122 102 20 12 2.48 Comparative Example 10 - 0.34 0.38 2.38 2.48 121 100 21 11 2.43 Comparative Example 11 - 0.13 0.13 0.78 0.79 174 158 16 9 1.84 Comparative Example 12 - 0.10 0.11 0.68 0.71 184 175 9 6 1.87 Comparative Example 13 - 0.15 0.15 0.82 0.83 151 158 -7 21 2.50 Comparative Example 14 - 0.30 0.27 1.51 1.74 133 138 -5 20 1.87 Comparative Example 15 - 0.12 0.13 1.42 1.43 169 160 9 8 1.85 Comparative Example 16 + 0.30 0.28 1.52 1.86 130 145 -15 3 9 2.80 Comparative Example 17 - 0.13 0.13 1.42 1.42 155 155 0 12 1.85 Comparative Example 18 + 0.31 0.28 1.51 1.78 128 133 -5 28 2.45 Comparative Example 19 - 0.12 0.13 1.42 1.43 175 178 -3 10 1.87 Comparative Example 20 - 0.14 0.16 1.01 1.12 150 149 1 9 2.23 Comparative Example 21 - 0.06 0.05 0.4 0.37 261 280 -19 38 2.73 18 201245471 According to Table 1 to Table 3, it is known that the polishing wheel with fine texture (abrasive grain) is used for a sufficient number of final heat treatments (he In the case of the respective examples of the pickling and polishing, the solder wettability is excellent and the pinholes are reduced. Each of the examples is {(6-degree specular gloss 〇 (RD) in the parallel direction of rolling) _ (60-degree specular gloss G (TD) in the direction of the right angle) } 90/. It is possible to sufficiently remove the oxide film and the foreign matter from the surface of the material and to smooth the surface. In addition, in each of the examples, pickling polishing is performed under the conditions that the abrasive grains have a particle size of 2 Å or more, the number of times of the plate is 2 or more, the plate speed is 10 mPm or less, and the number of rotations is 1200 rpm or more. The device is adapted to the best range of the application. In the other comparative examples, the pickling and polishing were not sufficiently performed, and the oxide film on the surface of the material or the press-in of the foreign matter could not be sufficiently removed. Therefore, in each comparative example, {(60-degree specular gloss g (RD)) in the parallel direction of rolling _ (6-degree specular gloss G (TD) in the direction of the right angle)) < 90 /. Further, the pinholes increase, and the oxide film remains excessively, resulting in deterioration of solder wettability. The reason for the deterioration of ''Xuan et al.') is in the case of Comparative Examples 1, 2, 丨5, 丨7, 丨9. ^ is due to the pickling and polishing of the plate speed exceeds 20 mpm. In the case of Comparative Examples 3, 5, 8, and 20, it was considered that the number of passes through the pickling and polishing was less than 2 times. Further, in Comparative Example 2, pickling and polishing were carried out by the above-described A method after the final rolling. In the case of Comparative Example 1, 3, it can be considered that the reason was that although the pickling was performed, the polishing was not performed. 19 201245471 In the case of Comparative Examples 6 and 7, it is considered that since the abrasive grains subjected to pickling polishing are 4000 grains and the abrasive grains are too fine, polishing is hardly performed, resulting in less Ra (RD) reduction effect. In the case of Comparative Examples 11 and 12, the reason was considered to be that the number of rotations of the pickling polishing was less than 1200 rpm. In the case of Comparative Example 9, 1 ,, the abrasive grains are too rough to cause pickling and polishing.

The light-polished surface is rough and makes {(6-degree specular gloss G (RD) in the parallel direction of rolling) - (6-degree specular gloss in the direction of the right angle) < 90% and leads to an increase in pinholes The difference is considered to be due to the fact that the abrasive grains subjected to pickling polishing are 5 Å in size, and thus the abrasive grains are too rough. In the case of Comparative Example 4, 14, 16, 18, and 2, it was considered that the surface state of the surface of the oxygen was not removed. Further, after the final rolling, the pickling and polishing of the film and the pressing of the foreign matter were carried out to maintain the original pressure. Comparative Example 21 was produced in the same manner as in the respective examples except that the roughness of the roll to be finally rolled was reduced. In addition, in the case of Comparative Example 1 6 and 18, since the treatment was carried out before the finish pressing (pickling or degreasing), and the pickling and polishing were not performed, the peak position was used as the average line for the roughness curve ( The position of the zero in the power distribution map indicating the unevenness of the surface is more on the positive side (the convex component side). That is, the core comparative example shows the copper alloy sheet of Patent Document 2. Further, in the case of Comparative Examples 4, 13, 16, and 21, the soldering time exceeded 2.0 seconds, and the solder wettability was also deteriorated, which is considered to be due to the fact that the pickling and polishing were not performed. Oxide film remains on the metal surface 20 201245471. (Comparative Example 1 6 corresponds to the conditions described in Patent Document 2) [Brief Description of the Drawings] Fig. 1 is a view showing an example of a manufacturing process of a Co-Si-based copper alloy sheet according to an embodiment of the present invention. Fig. 2 is a graph showing the degree distribution of the surface unevenness component of Example 4. Fig. 3 is a graph showing the degree distribution of the uneven component on the surface of Example 18. Ming said No. Symbol L , Main 2 Copper alloy plate 4 Pickling tank 6 Polishing wheel Ra Surface rough seam Rz Surface rough seam TD Calendering right angle direction RD Calendering parallel direction PI frequency P2 Frequency 21

Claims (1)

201245471 Qishen May patent range: Co-Si steel alloy plate containing Co: 0.5~3.0% by mass, Si 0·1~1.0% by mass and the remainder consisting of cu and unavoidable impurities, and {( 60 degree specular gloss G(RD) of the calendering parallel direction - (60 degrees specular gloss g(TD) in the direction of the right angle) 90%. 2. The Co-Si-based copper alloy sheet according to the first aspect of the patent application, wherein the surface roughness Ra(RD) of the rolling parallel direction is 0.07 //m. The invention discloses a Co-Si copper alloy plate according to item 2 of the patent scope, wherein the surface roughness Rz(RD) of the rolling parallel direction is $0.50 #m. 4. The Co_si-based steel alloy sheet according to any one of claims 1 to 3, wherein the peak position in the degree distribution map indicating the surface unevenness in the direction perpendicular to the rolling direction is located on the average line of the roughness curve. Negative side (concave component side). 5. The c〇_si gold plate of any one of the scopes of the fourth to fourth claims is selected from the group consisting of Mn, Fe, Ni, Cr'V, Nb, Mo. One or two or more of the group consisting of Zr, B, Ag, Be, Zn, Sn, thief, and P. twenty two