WO2011152104A1 - Cu-co-si-based alloy sheet, and process for production thereof - Google Patents
Cu-co-si-based alloy sheet, and process for production thereof Download PDFInfo
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- WO2011152104A1 WO2011152104A1 PCT/JP2011/057216 JP2011057216W WO2011152104A1 WO 2011152104 A1 WO2011152104 A1 WO 2011152104A1 JP 2011057216 W JP2011057216 W JP 2011057216W WO 2011152104 A1 WO2011152104 A1 WO 2011152104A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- the present invention relates to a Cu—Co—Si based alloy plate which is a precipitation hardening type copper alloy suitable for use in various electronic components, and more particularly to a Cu—Co—Si based alloy plate excellent in uniform adhesion of plating.
- Copper alloys for electronic materials used in various electronic parts such as connectors, switches, relays, pins, terminals, and lead frames are required to have both high strength and high conductivity (or thermal conductivity) as basic characteristics. Is done. In recent years, high integration and miniaturization / thinning of electronic components have been rapidly progressing, and the level of demand for copper alloys used in electronic device components has been increased accordingly.
- the amount of precipitation hardening type copper alloys is increasing instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass as copper alloys for electronic materials.
- precipitation-hardened copper alloys by aging the supersaturated solid solution that has undergone solution treatment, fine precipitates are uniformly dispersed, increasing the strength of the alloy and reducing the amount of solid solution elements in the copper. Electrical conductivity is improved. For this reason, a material excellent in mechanical properties such as strength and spring property and having good electrical conductivity and thermal conductivity can be obtained.
- Ni-Si copper alloys commonly called Corson alloys
- Corson alloys are representative copper alloys that have relatively high electrical conductivity, strength, and bending workability, and are currently being actively developed in the industry. Is one of the alloys that has been made. In this copper alloy, the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.
- Patent Document 1 for the purpose of a Ni—Si—Co based copper alloy having excellent bending workability, electrical conductivity, strength and stress relaxation resistance, the amounts of Ni, Si, Co and The mutual relationship is controlled, and the average crystal grain size of 20 ⁇ m or less is also described.
- the first aging annealing temperature is higher than the second aging annealing temperature (paragraphs 0045 to 0047).
- Patent Document 2 for the purpose of improving the bending workability of the Ni—Si—Co based copper alloy, the distribution state of the second phase particles is controlled to suppress the coarsening of the crystal grains. ing.
- this patent document for a copper alloy in which cobalt is added to a Corson alloy, the relationship between precipitates having an effect of suppressing the coarsening of crystal grains during high-temperature heat treatment and their distribution state is clarified, and the crystal grain size is controlled. Strength, conductivity, stress relaxation characteristics, and bending workability are improved (paragraph 0016). The smaller the crystal grain size, the better, and it is said that bending workability is improved by setting it to 10 ⁇ m or less (paragraph 0021).
- Patent Document 3 discloses a copper alloy for electronic materials in which generation of coarse second phase particles in a Ni—Si—Co based copper alloy is suppressed.
- Patent Document 3 by performing hot rolling and solution treatment under specific conditions, suppressing the generation of coarse second-phase particles, it is said that excellent properties can be achieved (paragraph 0012). .
- An object of the present invention is to provide a Cu—Co—Si based alloy plate to which base plating, in particular, Ni plating can uniformly adhere.
- the present inventor has obtained further foundation plating by replacing Ni with Co to form a Cu—Co—Si alloy in a Cu—Ni—Si alloy plate. It was found that the improvement of the adhesion of can be pursued. Furthermore, the surface layer of the Cu—Co—Si based alloy plate tends to be coarser locally than the inside (plate thickness center), and the presence of coarsened crystals on the surface makes it possible to increase the average grain size of the whole. It has been found that even if the diameter is small, the plating (uniform adhesion) property decreases.
- the present invention has the following configuration.
- the center average crystal grain size is 20 ⁇ m or less, and the number of crystal grains in contact with the surface and having a major axis of 45 ⁇ m or more is 5 or less with respect to a length of 1 mm in the rolling direction. Alloy plate.
- the added Co and Si form an intermetallic compound in the copper alloy by performing an appropriate heat treatment, and the conductivity is present despite the presence of additional elements other than copper.
- the strength can be increased by the precipitation strengthening effect without degrading. If the addition amounts of Co and Si are less than Co: 0.5 mass% and Si: less than 0.1 mass%, the desired strength cannot be obtained. On the contrary, if Co: more than 3.0 mass% and Si: more than 1.0 mass%, the strength can be increased, but the electrical conductivity is remarkably lowered, and further, the hot workability is degraded. Therefore, the addition amounts of Co and Si were set to Co: 0.5 to 3.0 mass% and Si: 0.1 to 1.0 mass%. The addition amounts of Co and Si are preferably Co: 0.5 to 2.0 mass% and Si: 0.1 to 0.5 mass%.
- the Cu—Co—Si based alloy plate according to the present invention can be added with one or two selected from Sn and Zn up to a maximum of 2.0 mass% in total. However, if the amount is less than 0.05% by mass, the effect is small. Therefore, the total amount is preferably 0.05 to 2.0% by mass, and more preferably 0.5 to 1.0% by mass in total.
- Addition amount of As, Sb, Be, B, Ti, Zr, Al, and Fe is determined according to the required product characteristics. By adjusting, product characteristics such as conductivity, strength, stress relaxation characteristics, and plating properties are improved. The effect of addition is exhibited mainly by solid solution in the parent phase, but it can also be exhibited by forming the second phase particles having a new composition or contained in the second phase particles. However, if the total amount of these elements exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired.
- the total amount of one or more selected from As, Sb, Be, B, Ti, Zr, Al and Fe is 2.0 mass in total. % Can be added. However, if the amount is less than 0.001% by mass, the effect is small. Therefore, the total amount is preferably 0.001 to 2.0% by mass, and more preferably 0.05 to 1.0% by mass. If the total amount of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag exceeds 2.0% by mass, manufacturability is likely to be impaired. Preferably, the total of these is 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less.
- the average crystal grain size at the center of the thickness of the cross section in the rolling direction is 20 ⁇ m or less.
- the average crystal grain size at the center of the plate thickness is measured based on JIS H 0501 (cutting method).
- the average crystal grain size at the center of the thickness of the copper alloy sheet of the present invention does not change significantly before and after the final rolling with a working degree of 10 to 50%. Therefore, if the average crystal grain size is 20 ⁇ m or less before the final rolling, a finer crystal structure than the sample copper alloy having an average crystal grain size of 20 ⁇ m is maintained even after the final rolling.
- a sample obtained by final rolling a sample having an average crystal grain size of 20 ⁇ m under the same conditions before the final rolling is standard. It can be determined whether or not the average crystal grain size exceeds 20 ⁇ m.
- the average crystal grain size of 20 ⁇ m or less at the center of the plate thickness is a rule for ensuring the same high strength as in the prior art, and “the center of the plate thickness” is a word for indicating the measurement position.
- the surface layer is most likely to accumulate strain energy in the rolling process, and the crystals are likely to be locally coarsened in the normal manufacturing conditions as compared with the inside (center of the plate thickness).
- the heat history may be different between the surface layer and the inside, and the crystal may be locally coarsened as compared with the inside (center of plate thickness).
- the “surface layer” here refers to a range of 25 ⁇ m from the surface.
- a copper alloy plate for electronic materials to which plating is uniformly attached can be obtained by reducing the number of coarse crystal grains on the surface of the Cu—Co—Si alloy plate.
- the number of crystal grains in contact with the surface and having a major axis after final rolling of 45 ⁇ m or more is 5 or less, preferably 4 or less, more preferably 2 with respect to a length of 1 mm in the rolling direction. It is the following. When the number exceeds 5, the plating does not adhere uniformly, and when the surface of the plating is viewed with the naked eye, it becomes a defective product in a state where clouding occurs.
- the number of crystal grains is determined by measuring the number of crystal grains of 45 ⁇ m or more in contact with the surface of the cross section in the rolling direction in a micrograph (magnification: ⁇ 400), and the length of the surface in multiple (10 times) measurement fields is 2000 ⁇ m. The number of crystal grains was divided by the total length in the range of 1 mm unit.
- the copper alloy plate of the present invention Since the copper alloy plate of the present invention has 5 or less crystal grains having a major axis of 45 ⁇ m or more on the surface, it is excellent in uniform adhesion of plating.
- Various plating materials can be applied to the copper alloy plate of the present invention, and examples thereof include Ni base plating, Cu base plating, and Sn plating that are usually used for the base of Au plating.
- the plating thickness of the present invention shows sufficient uniform adhesion even with a thickness of 0.5 to 2.0 ⁇ m as well as a thickness of 2 to 5 ⁇ m which is usually used.
- the manufacturing method of the copper alloy plate of the present invention is a general manufacturing process using a copper alloy plate (melting / casting ⁇ hot rolling ⁇ intermediate cold rolling ⁇ intermediate solution forming ⁇ final cold rolling ⁇ aging). In this process, the following conditions are adjusted to produce the target copper alloy sheet. In addition, about intermediate rolling and intermediate solution forming, you may repeat several times as needed. In the present invention, it is important to strictly control the conditions of hot rolling, intermediate cold rolling, and intermediate solution treatment. The reason for this is that the copper alloy plate of the present invention is added with Co, which tends to coarsen the second phase particles, and the generation and growth rate of the second phase particles greatly affects the holding temperature and cooling rate during the heat treatment. Because it is done.
- raw materials such as electrolytic copper, Si, and Co are melted to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot.
- this molten metal is cast into an ingot.
- hot rolling it is necessary to perform uniform heat treatment to eliminate crystallized substances such as Co—Si generated by casting as much as possible. For example, hot rolling is performed after holding at 950 ° C. to 1050 ° C. for 1 hour or longer. If the holding temperature before hot rolling is less than 950 ° C., solid solution is insufficient, while if it exceeds 1050 ° C., the material may be dissolved.
- finish of hot rolling is less than 700 degreeC, it means that the process of several passes including the last pass of a hot rolling or the last pass was performed at less than 700 degreeC.
- the temperature at the end of hot rolling is less than 700 ° C.
- the inside is in a recrystallized state, whereas the surface layer is finished in a state where it is subjected to processing strain.
- the inside is a normal recrystallized structure, whereas the surface layer is formed with coarse crystal grains. Therefore, in order to prevent the formation of coarse crystals on the surface layer, it is desirable to finish the hot rolling at 700 ° C. or higher, preferably 850 ° C. or higher, and to cool rapidly after the hot rolling is finished. Rapid cooling can be achieved by water cooling.
- intermediate rolling and intermediate solution forming are performed by appropriately selecting the number of times and the order within the target range. If the degree of processing in the final pass of the intermediate rolling is less than 5%, processing strain energy is accumulated only on the material surface, and coarse crystal grains are generated on the surface layer. In particular, the intermediate rolling degree of the final pass is preferably 8% or more. In addition, controlling the viscosity of the rolling oil used in the intermediate rolling and the speed of the intermediate rolling is also effective for uniformly applying the processing strain energy.
- the intermediate solution treatment is carried out sufficiently to dissolve the crystallized particles at the time of melt casting and the precipitated particles after hot rolling so as to eliminate as coarse a Co—Si precipitate as possible.
- the solution treatment temperature is less than 850 ° C.
- the solid solution is insufficient and the desired strength cannot be obtained.
- the solution treatment temperature exceeds 1050 ° C.
- the material may be dissolved. Therefore, it is preferable to perform a solution treatment in which the material temperature is heated to 850 ° C. to 1050 ° C.
- the solution treatment time is preferably 0.5 minutes to 1 hour. It should be noted that, as a relationship between temperature and time, in order to obtain the same heat treatment effect (for example, the same crystal grain size), it is common knowledge that the time should be short at high temperatures and long at low temperatures.
- the cooling rate after the solution treatment is generally quenched in order to prevent precipitation of solid solution second phase particles.
- an aging treatment is performed under a temperature condition of 400 ° C. or more and 600 ° C. or less to precipitate fine second phase particles uniformly. If the aging temperature is less than 400 ° C., the second phase particles are not sufficiently precipitated, and the desired strength and electrical conductivity cannot be obtained. This is because the particles are coarsened and a desired strength cannot be obtained.
- the aging temperature is preferably 450 ° C. or higher and 550 ° C. or lower.
- the degree of work of the final rolling is preferably 10 to 50%, preferably 30 to 50%. If it is less than 10%, the desired strength cannot be obtained. On the other hand, when it exceeds 50%, bending workability deteriorates.
- the copper alloy plate of the present invention has no coarse crystal particles on the surface, it has excellent uniform plating adhesion, and is suitable for electronic parts such as lead frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries. Can be used for
- Crystal grain size at the center of the plate thickness Standard sample (Co: 1.0 mass%, average grain size of 20 ⁇ m at the center of the plate thickness in the rolling direction after the solution treatment and before final rolling Si: 0.66 mass%, balance copper) was produced. The average crystal grain size was measured based on JIS H 0501 (cutting method). The standard sample was subjected to final cold rolling (working degree 15%), and an optical micrograph (magnification: ⁇ 400) of the center of the thickness in the cross section in the rolling direction was taken as a reference.
- optical micrograph (same magnification as the standard) of the center of the thickness after the final cold rolling of each example (invention example and comparative example) and the size of the standard are visually compared, and if larger, larger than 20 ⁇ m ( > 20 ⁇ m), and when equal or smaller, 20 ⁇ m or less ( ⁇ 20 ⁇ m).
- Electrolytic degreasing is performed using a sample as a cathode in an alkaline aqueous solution. Pickling is performed using a 10% by mass aqueous sulfuric acid solution.
- -Plating bath composition nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L ⁇ Plating bath temperature: 50 °C ⁇
- Current density 5 A / dm 2 -Ni plating thickness was adjusted with the electrodeposition time, and was 1.0 micrometer. The plating thickness was measured using a CT-1 type electrolytic film thickness meter (manufactured by Denso Co., Ltd.) and an electrolytic solution R-54 manufactured by Kocourt.
- FIG. 1 is an optical micrograph of the plating surface of Example 1 of the present invention, which corresponds to “S” rank
- FIG. 2 is an optical micrograph of the plating surface of Comparative Example 11, and ranks “C”. Equivalent to.
- FIG. 3 is an enlarged photograph (magnification: ⁇ 2500) of “island-like plating” observed on the plating surface, and the number of island-like platings in the field of view was measured using such an island shape as one.
- E Conductivity (EC;% IACS) The volume resistivity was measured by a double bridge.
- F Bending workability In accordance with JIS H 3130, a badway (bending axis is the same direction as the rolling direction) is subjected to a W-bending test, and MBR, which is a ratio of a minimum radius (MBR) to a thickness (t) at which no cracks occur. / T value was measured. Bending workability was evaluated according to the following criteria. MBR / t ⁇ 2.0 Good 2.0 ⁇ MBR / t Poor
- Comparative Example 12 Compared to 15% of the degree of intermediate rolling in the final pass of Comparative Example 11, it is as low as 5% in Comparative Example 12 having the same composition, so that coarse particles are further generated on the surface, resulting in poor uniform plating adhesion.
- the hot rolling start temperature of Invention Example 7 is 950 ° C.
- the ascending temperature is 750 ° C.
- the processing degree of intermediate rolling in the final pass is 15%. Therefore, coarse particles are generated on the surface, resulting in poor uniform plating adhesion.
- the relationship between Invention Example 8 and Comparative Example 18 is the same.
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Abstract
Disclosed is a Cu-Co-Si-based alloy sheet which can be used suitably for various electronic components and can be plated satisfactorily and homogeneously. Specifically disclosed is a copper alloy sheet for an electronic material, which comprises 0.5 to 3.0 mass% of Co, 0.1 to 1.0 mass% of Si, and a remainder made up by Cu and unavoidable impurities, wherein the average crystal particle diameter at the thicknesswise center part of the sheet is 20 μm or less and crystal particles that are in contact with the surface of the sheet and have a longer diameter of 45 μm or less exist at a density of 5 particles or less per mm of the length of the sheet in the rolling direction.
Description
本発明は各種電子部品に用いるのに好適な析出硬化型銅合金であるＣｕ－Ｃｏ－Ｓｉ系合金板に関し、とりわけ、めっきの均一付着性に優れたＣｕ－Ｃｏ－Ｓｉ系合金板に関する。
The present invention relates to a Cu—Co—Si based alloy plate which is a precipitation hardening type copper alloy suitable for use in various electronic components, and more particularly to a Cu—Co—Si based alloy plate excellent in uniform adhesion of plating.
コネクタ、スイッチ、リレー、ピン、端子、リードフレーム等の各種電子部品に使用される電子材料用銅合金には、基本特性として高強度及び高導電性（又は熱伝導性）を両立させることが要求される。近年、電子部品の高集積化及び小型化・薄肉化が急速に進み、これに対応して電子機器部品に使用される銅合金に対する要求レベルはますます高度化している。
Copper alloys for electronic materials used in various electronic parts such as connectors, switches, relays, pins, terminals, and lead frames are required to have both high strength and high conductivity (or thermal conductivity) as basic characteristics. Is done. In recent years, high integration and miniaturization / thinning of electronic components have been rapidly progressing, and the level of demand for copper alloys used in electronic device components has been increased accordingly.
高強度及び高導電性の観点から、電子材料用銅合金として従来のりん青銅、黄銅等に代表される固溶強化型銅合金に替わり、析出硬化型の銅合金の使用量が増加している。析出硬化型銅合金では、溶体化処理された過飽和固溶体を時効処理することにより、微細な析出物が均一に分散して、合金の強度が高くなると同時に、銅中の固溶元素量が減少し電気伝導性が向上する。このため、強度、ばね性などの機械的性質に優れ、しかも電気伝導性、熱伝導性が良好な材料が得られる。
From the viewpoint of high strength and high conductivity, the amount of precipitation hardening type copper alloys is increasing instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass as copper alloys for electronic materials. . In precipitation-hardened copper alloys, by aging the supersaturated solid solution that has undergone solution treatment, fine precipitates are uniformly dispersed, increasing the strength of the alloy and reducing the amount of solid solution elements in the copper. Electrical conductivity is improved. For this reason, a material excellent in mechanical properties such as strength and spring property and having good electrical conductivity and thermal conductivity can be obtained.
析出硬化型銅合金のうち、コルソン系合金と一般に呼ばれるＮｉ－Ｓｉ系銅合金は比較的高い導電性、強度、及び曲げ加工性を兼備する代表的な銅合金であり、業界において現在活発に開発が行われている合金の一つである。この銅合金では、銅マトリックス中に微細なＮｉ－Ｓｉ系金属間化合物粒子を析出させることによって強度と導電率の向上が図れる。
Of precipitation hardening copper alloys, Ni-Si copper alloys, commonly called Corson alloys, are representative copper alloys that have relatively high electrical conductivity, strength, and bending workability, and are currently being actively developed in the industry. Is one of the alloys that has been made. In this copper alloy, the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.
コルソン合金の更なる特性の向上を目的として、Ｎｉ及びＳｉ以外の合金成分の添加、特性に悪影響を与える成分の排除、結晶組織の最適化、析出粒子の最適化といった各種の技術開発がなされている。例えば、Ｃｏを添加することや母相中に析出する第二相粒子を制御することによって特性が向上することが知られており、Ｎｉ－Ｓｉ－Ｃｏ系銅合金の最近の改良技術としては以下のようなものが挙げられる。
In order to further improve the properties of the Corson alloy, various technological developments have been made such as addition of alloy components other than Ni and Si, elimination of components that adversely affect the properties, optimization of the crystal structure, and optimization of the precipitated particles. Yes. For example, it is known that the characteristics are improved by adding Co or controlling the second phase particles precipitated in the matrix phase. The recent improvement techniques for Ni—Si—Co based copper alloys include the following: The thing like this is mentioned.
特表２００５－５３２４７７号公報（特許文献１）では、曲げ加工性、導電率、強度及び耐応力弛緩性に優れたＮｉ－Ｓｉ－Ｃｏ系銅合金を目的として、Ｎｉ、Ｓｉ、Ｃｏ量及びその互いの関係を制御しており、２０μｍ以下の平均結晶粒径についても記載されている。そしてその製造工程においては、第一の時効焼鈍温度が第２の時効焼鈍温度よりも高いことを特徴とする（段落００４５～００４７）。
In JP 2005-532477 A (Patent Document 1), for the purpose of a Ni—Si—Co based copper alloy having excellent bending workability, electrical conductivity, strength and stress relaxation resistance, the amounts of Ni, Si, Co and The mutual relationship is controlled, and the average crystal grain size of 20 μm or less is also described. In the manufacturing process, the first aging annealing temperature is higher than the second aging annealing temperature (paragraphs 0045 to 0047).
特開２００７－１６９７６５号公報（特許文献２）では、Ｎｉ－Ｓｉ－Ｃｏ系銅合金の曲げ加工性の向上を目的として第２相粒子の分布状態を制御して結晶粒の粗大化を抑制している。この特許文献では、コルソン合金にコバルトを添加した銅合金について、高温熱処理における結晶粒の粗大化を抑制する効果をもつ析出物とその分布状態の関係を明らかにし、結晶粒径を制御することにより強度、導電性、応力緩和特性、曲げ加工性を向上させている（段落００１６）。結晶粒径は小さければ小さいほど好ましく、１０μｍ以下とすることにより曲げ加工性が向上するとされている（段落００２１）。
In Japanese Patent Application Laid-Open No. 2007-169765 (Patent Document 2), for the purpose of improving the bending workability of the Ni—Si—Co based copper alloy, the distribution state of the second phase particles is controlled to suppress the coarsening of the crystal grains. ing. In this patent document, for a copper alloy in which cobalt is added to a Corson alloy, the relationship between precipitates having an effect of suppressing the coarsening of crystal grains during high-temperature heat treatment and their distribution state is clarified, and the crystal grain size is controlled. Strength, conductivity, stress relaxation characteristics, and bending workability are improved (paragraph 0016). The smaller the crystal grain size, the better, and it is said that bending workability is improved by setting it to 10 μm or less (paragraph 0021).
特開２００８－２４８３３３号公報（特許文献３）では、Ｎｉ－Ｓｉ－Ｃｏ系銅合金中の粗大な第二相粒子の発生を抑制した電子材料用銅合金が開示されている。この特許文献では、熱間圧延及び溶体化処理を特定の条件下で行うことによって、粗大な第二相粒子の発生を抑制すると、目的の優れた特性が実現出来るとされている（段落００１２）。
Japanese Patent Laid-Open No. 2008-248333 (Patent Document 3) discloses a copper alloy for electronic materials in which generation of coarse second phase particles in a Ni—Si—Co based copper alloy is suppressed. In this patent document, by performing hot rolling and solution treatment under specific conditions, suppressing the generation of coarse second-phase particles, it is said that excellent properties can be achieved (paragraph 0012). .
通常、コネクタ、スイッチ、リレー、ピン、端子、リードフレーム等の各種電子部品に使用される電子材料用銅合金板は、Ａｕめっきを施されることが多いが、その際、下地としてＮｉめっきが施されることが一般的である。このＮｉ下地めっきについても近年の部品の軽量化・薄肉化につれて薄くなってきている。
そこで、これまで問題とならなかったようなＮｉめっきの不具合、具体的には、Ｎｉめっきが部分的に均一につかないという不具合が顕在化してきた。 Usually, copper alloy plates for electronic materials used for various electronic parts such as connectors, switches, relays, pins, terminals, lead frames, etc. are often plated with Au. It is common to apply. This Ni base plating is also becoming thinner as the weight and thickness of parts are reduced in recent years.
Therefore, a defect of Ni plating that has not been a problem until now, specifically, a defect that Ni plating cannot be applied partially uniformly has become apparent.
そこで、これまで問題とならなかったようなＮｉめっきの不具合、具体的には、Ｎｉめっきが部分的に均一につかないという不具合が顕在化してきた。 Usually, copper alloy plates for electronic materials used for various electronic parts such as connectors, switches, relays, pins, terminals, lead frames, etc. are often plated with Au. It is common to apply. This Ni base plating is also becoming thinner as the weight and thickness of parts are reduced in recent years.
Therefore, a defect of Ni plating that has not been a problem until now, specifically, a defect that Ni plating cannot be applied partially uniformly has become apparent.
上記特許文献１～３に記載の銅合金は、いずれも結晶粒径については記載されているが、深さ方向での結晶粒径のバラツキ、特に表面に形成される粗大結晶とめっきの付着性との関係については全く意識されていない。
本発明の課題は、下地めっき、特にＮｉめっきが均一に付着できるＣｕ－Ｃｏ－Ｓｉ系合金板を提供することにある。 The copper alloys described in Patent Documents 1 to 3 are all described in terms of the crystal grain size, but the crystal grain size variation in the depth direction, particularly the adhesion between the coarse crystal formed on the surface and the plating I am not conscious of the relationship at all.
An object of the present invention is to provide a Cu—Co—Si based alloy plate to which base plating, in particular, Ni plating can uniformly adhere.
本発明の課題は、下地めっき、特にＮｉめっきが均一に付着できるＣｕ－Ｃｏ－Ｓｉ系合金板を提供することにある。 The copper alloys described in Patent Documents 1 to 3 are all described in terms of the crystal grain size, but the crystal grain size variation in the depth direction, particularly the adhesion between the coarse crystal formed on the surface and the plating I am not conscious of the relationship at all.
An object of the present invention is to provide a Cu—Co—Si based alloy plate to which base plating, in particular, Ni plating can uniformly adhere.
本発明者は、上記課題を解決するために研究を重ねた結果、Ｃｕ－Ｎｉ－Ｓｉ系合金板において、ＮｉをＣｏに置き換えてＣｕ－Ｃｏ－Ｓｉ系合金とすることにより、さらなる下地めっきとの密着性の改善が追求できることがわかった。さらに当該Ｃｕ－Ｃｏ－Ｓｉ系合金板の表層は内部（板厚中心）に比べて局部的に結晶粒径が粗大化しやすく、表面に粗大化結晶が存在することにより、たとえ全体の平均結晶粒径は小さくてもめっき（均一付着）性が低下してしまうことを見出した。本発明は、下記の構成を有する。
（１）Ｃｏ：０．５～３．０質量％、Ｓｉ：０．１～１．０質量％を含有し、残部がＣｕ及び不可避不純物からなる電子材料用銅合金板であって、板厚中心の平均結晶粒径が２０μｍ以下で、表面に接した結晶粒でかつ長径が４５μｍ以上の結晶粒が、圧延方向長さ１ｍｍに対して５個以下であることを特徴とする電子材料用銅合金板。
（２）更にＣｒを最大０．５質量％含有する（１）記載の電子材料用銅合金板。
（３）更にＭｇ、Ｐ、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｍｎ、Ｓｎ、Ｔｉ、Ｚｒ、Ａｌ、Ｆｅ、Ｚｎ及びＡｇよりなる群から選ばれる１種又は２種以上を総計で最大２．０質量％含有する（１）又は（２）記載の電子材料用銅合金板。
（４）インゴットを溶解鋳造する工程と、
材料温度を９５０℃以上１０５０℃以下として１時間以上加熱後に、熱間圧延を行い、熱間圧延終了温度が７００℃以上である工程と、
最終パスが８％以上の加工度で行われる溶体化前の中間圧延工程と、
材料温度を８５０℃以上１０５０℃以下で０．５分～１時間加熱する中間溶体化工程と、
４００℃以上６００℃以下で加熱する時効工程と、
加工度１０～５０％の最終圧延工程と、
をこの順で行うことを含む（１）～（３）いずれか記載の電子材料用銅合金板の製造方法。 As a result of repeated researches to solve the above-mentioned problems, the present inventor has obtained further foundation plating by replacing Ni with Co to form a Cu—Co—Si alloy in a Cu—Ni—Si alloy plate. It was found that the improvement of the adhesion of can be pursued. Furthermore, the surface layer of the Cu—Co—Si based alloy plate tends to be coarser locally than the inside (plate thickness center), and the presence of coarsened crystals on the surface makes it possible to increase the average grain size of the whole. It has been found that even if the diameter is small, the plating (uniform adhesion) property decreases. The present invention has the following configuration.
(1) A copper alloy plate for electronic materials containing Co: 0.5 to 3.0% by mass, Si: 0.1 to 1.0% by mass, the balance being Cu and inevitable impurities, The center average crystal grain size is 20 μm or less, and the number of crystal grains in contact with the surface and having a major axis of 45 μm or more is 5 or less with respect to a length of 1 mm in the rolling direction. Alloy plate.
(2) The copper alloy plate for electronic materials according to (1), further containing 0.5 mass% of Cr at the maximum.
(3) Furthermore, one or two or more selected from the group consisting of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag in total up to 2.0 The copper alloy plate for electronic materials according to (1) or (2), which is contained by mass.
(4) melting and casting the ingot;
A process in which the material temperature is set to 950 ° C. or higher and 1050 ° C. or lower and heated for 1 hour or longer, followed by hot rolling, and the hot rolling end temperature is 700 ° C. or higher;
An intermediate rolling step before solution treatment in which the final pass is performed at a working degree of 8% or more;
An intermediate solution forming step of heating at a material temperature of 850 ° C. to 1050 ° C. for 0.5 minutes to 1 hour;
An aging step of heating at 400 ° C. or higher and 600 ° C. or lower;
A final rolling step with a working degree of 10-50%,
The method for producing a copper alloy sheet for electronic materials according to any one of (1) to (3), comprising performing the steps in this order.
（１）Ｃｏ：０．５～３．０質量％、Ｓｉ：０．１～１．０質量％を含有し、残部がＣｕ及び不可避不純物からなる電子材料用銅合金板であって、板厚中心の平均結晶粒径が２０μｍ以下で、表面に接した結晶粒でかつ長径が４５μｍ以上の結晶粒が、圧延方向長さ１ｍｍに対して５個以下であることを特徴とする電子材料用銅合金板。
（２）更にＣｒを最大０．５質量％含有する（１）記載の電子材料用銅合金板。
（３）更にＭｇ、Ｐ、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｍｎ、Ｓｎ、Ｔｉ、Ｚｒ、Ａｌ、Ｆｅ、Ｚｎ及びＡｇよりなる群から選ばれる１種又は２種以上を総計で最大２．０質量％含有する（１）又は（２）記載の電子材料用銅合金板。
（４）インゴットを溶解鋳造する工程と、
材料温度を９５０℃以上１０５０℃以下として１時間以上加熱後に、熱間圧延を行い、熱間圧延終了温度が７００℃以上である工程と、
最終パスが８％以上の加工度で行われる溶体化前の中間圧延工程と、
材料温度を８５０℃以上１０５０℃以下で０．５分～１時間加熱する中間溶体化工程と、
４００℃以上６００℃以下で加熱する時効工程と、
加工度１０～５０％の最終圧延工程と、
をこの順で行うことを含む（１）～（３）いずれか記載の電子材料用銅合金板の製造方法。 As a result of repeated researches to solve the above-mentioned problems, the present inventor has obtained further foundation plating by replacing Ni with Co to form a Cu—Co—Si alloy in a Cu—Ni—Si alloy plate. It was found that the improvement of the adhesion of can be pursued. Furthermore, the surface layer of the Cu—Co—Si based alloy plate tends to be coarser locally than the inside (plate thickness center), and the presence of coarsened crystals on the surface makes it possible to increase the average grain size of the whole. It has been found that even if the diameter is small, the plating (uniform adhesion) property decreases. The present invention has the following configuration.
(1) A copper alloy plate for electronic materials containing Co: 0.5 to 3.0% by mass, Si: 0.1 to 1.0% by mass, the balance being Cu and inevitable impurities, The center average crystal grain size is 20 μm or less, and the number of crystal grains in contact with the surface and having a major axis of 45 μm or more is 5 or less with respect to a length of 1 mm in the rolling direction. Alloy plate.
(2) The copper alloy plate for electronic materials according to (1), further containing 0.5 mass% of Cr at the maximum.
(3) Furthermore, one or two or more selected from the group consisting of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag in total up to 2.0 The copper alloy plate for electronic materials according to (1) or (2), which is contained by mass.
(4) melting and casting the ingot;
A process in which the material temperature is set to 950 ° C. or higher and 1050 ° C. or lower and heated for 1 hour or longer, followed by hot rolling, and the hot rolling end temperature is 700 ° C. or higher;
An intermediate rolling step before solution treatment in which the final pass is performed at a working degree of 8% or more;
An intermediate solution forming step of heating at a material temperature of 850 ° C. to 1050 ° C. for 0.5 minutes to 1 hour;
An aging step of heating at 400 ° C. or higher and 600 ° C. or lower;
A final rolling step with a working degree of 10-50%,
The method for producing a copper alloy sheet for electronic materials according to any one of (1) to (3), comprising performing the steps in this order.
（１）Ｃｏ及びＳｉの添加量
添加されたＣｏ及びＳｉは、適当な熱処理を施すことにより、銅合金内で金属間化合物を形成し、銅以外の添加元素が存在するにも拘わらず導電率を劣化させずに、析出強化効果により高強度化が図れる。
Ｃｏ及びＳｉの添加量がそれぞれＣｏ：０．５質量％未満、Ｓｉ：０．１質量％未満では所望の強度が得られない。逆にＣｏ：３．０質量％超、Ｓｉ：１．０質量％超では、高強度化は図れるが導電率が著しく低下し、更には熱間加工性が劣化する。よって、Ｃｏ及びＳｉの添加量はＣｏ：０．５～３．０質量％、Ｓｉ：０．１～１．０質量％とした。Ｃｏ及びＳｉの添加量は好ましくは、Ｃｏ：０．５～２．０質量％、Ｓｉ：０．１～０．５質量％である。 (1) Addition amount of Co and Si The added Co and Si form an intermetallic compound in the copper alloy by performing an appropriate heat treatment, and the conductivity is present despite the presence of additional elements other than copper. The strength can be increased by the precipitation strengthening effect without degrading.
If the addition amounts of Co and Si are less than Co: 0.5 mass% and Si: less than 0.1 mass%, the desired strength cannot be obtained. On the contrary, if Co: more than 3.0 mass% and Si: more than 1.0 mass%, the strength can be increased, but the electrical conductivity is remarkably lowered, and further, the hot workability is degraded. Therefore, the addition amounts of Co and Si were set to Co: 0.5 to 3.0 mass% and Si: 0.1 to 1.0 mass%. The addition amounts of Co and Si are preferably Co: 0.5 to 2.0 mass% and Si: 0.1 to 0.5 mass%.
添加されたＣｏ及びＳｉは、適当な熱処理を施すことにより、銅合金内で金属間化合物を形成し、銅以外の添加元素が存在するにも拘わらず導電率を劣化させずに、析出強化効果により高強度化が図れる。
Ｃｏ及びＳｉの添加量がそれぞれＣｏ：０．５質量％未満、Ｓｉ：０．１質量％未満では所望の強度が得られない。逆にＣｏ：３．０質量％超、Ｓｉ：１．０質量％超では、高強度化は図れるが導電率が著しく低下し、更には熱間加工性が劣化する。よって、Ｃｏ及びＳｉの添加量はＣｏ：０．５～３．０質量％、Ｓｉ：０．１～１．０質量％とした。Ｃｏ及びＳｉの添加量は好ましくは、Ｃｏ：０．５～２．０質量％、Ｓｉ：０．１～０．５質量％である。 (1) Addition amount of Co and Si The added Co and Si form an intermetallic compound in the copper alloy by performing an appropriate heat treatment, and the conductivity is present despite the presence of additional elements other than copper. The strength can be increased by the precipitation strengthening effect without degrading.
If the addition amounts of Co and Si are less than Co: 0.5 mass% and Si: less than 0.1 mass%, the desired strength cannot be obtained. On the contrary, if Co: more than 3.0 mass% and Si: more than 1.0 mass%, the strength can be increased, but the electrical conductivity is remarkably lowered, and further, the hot workability is degraded. Therefore, the addition amounts of Co and Si were set to Co: 0.5 to 3.0 mass% and Si: 0.1 to 1.0 mass%. The addition amounts of Co and Si are preferably Co: 0.5 to 2.0 mass% and Si: 0.1 to 0.5 mass%.
（２）Ｃｒの添加量
Ｃｒは溶解鋳造時の冷却過程において、結晶粒界に優先的に析出するため粒界を強化でき、熱間加工時の割れが発生しにくくなり、製造時の歩留低下を抑制できる。すなわち、溶解鋳造時に粒界析出したＣｒは溶体化処理などで再固溶するが、続く時効析出時にＣｒを主成分としたｂｃｃ構造の析出粒子又はＳｉとの化合物（珪化物）を生成する。通常のＮｉ－Ｓｉ系銅合金では添加したＳｉ量のうち、時効析出に寄与しなかったＳｉは母相に固溶したまま残存し、導電率低下の原因となる。そこで、珪化物形成元素であるＣｒを添加して、時効析出に寄与しなかったＳｉを珪化物としてさらに析出させることにより、固溶Ｓｉ量を低減でき、強度を損なわずに導電率低下を防止できる。しかしながら、Ｃｒ濃度が０．５質量％を超えると粗大な第二相粒子を形成しやすくなるため、製品特性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金には、Ｃｒを最大で０．５質量％添加することができる。但し、０．０１質量％未満ではその効果が小さいので、好ましくは０．０１～０．５質量％、より好ましくは０．０９～０．３質量％添加するのがよい。 (2) Amount of Cr added Cr precipitates preferentially at the grain boundaries during the cooling process during melt casting, so the grain boundaries can be strengthened and cracks during hot working are less likely to occur, yielding during production. Reduction can be suppressed. That is, Cr precipitated at the grain boundary during melt casting is re-dissolved by solution treatment or the like, but at the subsequent aging precipitation, precipitated particles having a bcc structure mainly composed of Cr or a compound with Si (silicide) are generated. In a normal Ni—Si based copper alloy, of the amount of Si added, Si that has not contributed to aging precipitation remains in the mother phase as a solid solution, causing a decrease in conductivity. Therefore, by adding Cr, which is a silicide-forming element, and further precipitating Si that did not contribute to aging precipitation as a silicide, the amount of dissolved Si can be reduced, preventing a decrease in conductivity without losing strength. it can. However, when the Cr concentration exceeds 0.5% by mass, coarse second-phase particles are easily formed, so that product characteristics are impaired. Therefore, Cr can be added to the Cu—Co—Si alloy according to the present invention at a maximum of 0.5 mass%. However, since the effect is small if it is less than 0.01% by mass, it is preferably added in an amount of 0.01 to 0.5% by mass, more preferably 0.09 to 0.3% by mass.
Ｃｒは溶解鋳造時の冷却過程において、結晶粒界に優先的に析出するため粒界を強化でき、熱間加工時の割れが発生しにくくなり、製造時の歩留低下を抑制できる。すなわち、溶解鋳造時に粒界析出したＣｒは溶体化処理などで再固溶するが、続く時効析出時にＣｒを主成分としたｂｃｃ構造の析出粒子又はＳｉとの化合物（珪化物）を生成する。通常のＮｉ－Ｓｉ系銅合金では添加したＳｉ量のうち、時効析出に寄与しなかったＳｉは母相に固溶したまま残存し、導電率低下の原因となる。そこで、珪化物形成元素であるＣｒを添加して、時効析出に寄与しなかったＳｉを珪化物としてさらに析出させることにより、固溶Ｓｉ量を低減でき、強度を損なわずに導電率低下を防止できる。しかしながら、Ｃｒ濃度が０．５質量％を超えると粗大な第二相粒子を形成しやすくなるため、製品特性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金には、Ｃｒを最大で０．５質量％添加することができる。但し、０．０１質量％未満ではその効果が小さいので、好ましくは０．０１～０．５質量％、より好ましくは０．０９～０．３質量％添加するのがよい。 (2) Amount of Cr added Cr precipitates preferentially at the grain boundaries during the cooling process during melt casting, so the grain boundaries can be strengthened and cracks during hot working are less likely to occur, yielding during production. Reduction can be suppressed. That is, Cr precipitated at the grain boundary during melt casting is re-dissolved by solution treatment or the like, but at the subsequent aging precipitation, precipitated particles having a bcc structure mainly composed of Cr or a compound with Si (silicide) are generated. In a normal Ni—Si based copper alloy, of the amount of Si added, Si that has not contributed to aging precipitation remains in the mother phase as a solid solution, causing a decrease in conductivity. Therefore, by adding Cr, which is a silicide-forming element, and further precipitating Si that did not contribute to aging precipitation as a silicide, the amount of dissolved Si can be reduced, preventing a decrease in conductivity without losing strength. it can. However, when the Cr concentration exceeds 0.5% by mass, coarse second-phase particles are easily formed, so that product characteristics are impaired. Therefore, Cr can be added to the Cu—Co—Si alloy according to the present invention at a maximum of 0.5 mass%. However, since the effect is small if it is less than 0.01% by mass, it is preferably added in an amount of 0.01 to 0.5% by mass, more preferably 0.09 to 0.3% by mass.
（３）第３元素の添加量
ａ）Ｍｇ、Ｍｎ、Ａｇ及びＰの添加量
Ｍｇ、Ｍｎ、Ａｇ及びＰは、微量の添加で、導電率を損なわずに強度、応力緩和特性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有されることで一層の効果を発揮させることもできる。しかしながら、Ｍｇ、Ｍｎ、Ａｇ及びＰの濃度の総計が２．０質量％を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金板には、Ｍｇ、Ｍｎ、Ａｇ及びＰから選択される１種又は２種以上を総計で最大２．０質量％添加するのが好ましい。但し、０．０１質量％未満ではその効果が小さいので、より好ましくは総計で０．０１～２．０質量％、更により好ましくは総計で０．０２～０．５質量％、典型的には総計で０．０４～０．２質量％添加する。 (3) Addition amount of the third element a) Addition amounts of Mg, Mn, Ag and P Mg, Mn, Ag and P are added in a small amount, and product characteristics such as strength and stress relaxation characteristics without impairing electrical conductivity. To improve. The effect of addition is exhibited mainly by solid solution in the matrix phase, but further effects can be exhibited by inclusion in the second phase particles. However, if the total concentration of Mg, Mn, Ag and P exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, it is preferable to add a maximum of 2.0 mass% of one or more selected from Mg, Mn, Ag and P to the Cu—Co—Si based alloy sheet according to the present invention. However, since the effect is small at less than 0.01% by mass, more preferably 0.01 to 2.0% by mass in total, still more preferably 0.02 to 0.5% by mass in total, typically Add 0.04 to 0.2 mass% in total.
ａ）Ｍｇ、Ｍｎ、Ａｇ及びＰの添加量
Ｍｇ、Ｍｎ、Ａｇ及びＰは、微量の添加で、導電率を損なわずに強度、応力緩和特性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有されることで一層の効果を発揮させることもできる。しかしながら、Ｍｇ、Ｍｎ、Ａｇ及びＰの濃度の総計が２．０質量％を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金板には、Ｍｇ、Ｍｎ、Ａｇ及びＰから選択される１種又は２種以上を総計で最大２．０質量％添加するのが好ましい。但し、０．０１質量％未満ではその効果が小さいので、より好ましくは総計で０．０１～２．０質量％、更により好ましくは総計で０．０２～０．５質量％、典型的には総計で０．０４～０．２質量％添加する。 (3) Addition amount of the third element a) Addition amounts of Mg, Mn, Ag and P Mg, Mn, Ag and P are added in a small amount, and product characteristics such as strength and stress relaxation characteristics without impairing electrical conductivity. To improve. The effect of addition is exhibited mainly by solid solution in the matrix phase, but further effects can be exhibited by inclusion in the second phase particles. However, if the total concentration of Mg, Mn, Ag and P exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, it is preferable to add a maximum of 2.0 mass% of one or more selected from Mg, Mn, Ag and P to the Cu—Co—Si based alloy sheet according to the present invention. However, since the effect is small at less than 0.01% by mass, more preferably 0.01 to 2.0% by mass in total, still more preferably 0.02 to 0.5% by mass in total, typically Add 0.04 to 0.2 mass% in total.
ｂ）Ｓｎ及びＺｎの添加量
Ｓｎ及びＺｎにおいても、微量の添加で、導電率を損なわずに強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮される。しかしながら、Ｓｎ及びＺｎの総計が２．０質量％を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金板には、Ｓｎ及びＺｎから選択される１種又は２種を総計で最大２．０質量％添加することができる。但し、０．０５質量％未満ではその効果が小さいので、好ましくは総計で０．０５～２．０質量％、より好ましくは総計で０．５～１．０質量％添加するのがよい。 b) Addition amount of Sn and Zn Even in a small amount of Sn and Zn, product characteristics such as strength, stress relaxation characteristics, and plating properties are improved without impairing electrical conductivity. The effect of addition is exhibited mainly by solid solution in the matrix. However, if the total amount of Sn and Zn exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, the Cu—Co—Si based alloy plate according to the present invention can be added with one or two selected from Sn and Zn up to a maximum of 2.0 mass% in total. However, if the amount is less than 0.05% by mass, the effect is small. Therefore, the total amount is preferably 0.05 to 2.0% by mass, and more preferably 0.5 to 1.0% by mass in total.
Ｓｎ及びＺｎにおいても、微量の添加で、導電率を損なわずに強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮される。しかしながら、Ｓｎ及びＺｎの総計が２．０質量％を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金板には、Ｓｎ及びＺｎから選択される１種又は２種を総計で最大２．０質量％添加することができる。但し、０．０５質量％未満ではその効果が小さいので、好ましくは総計で０．０５～２．０質量％、より好ましくは総計で０．５～１．０質量％添加するのがよい。 b) Addition amount of Sn and Zn Even in a small amount of Sn and Zn, product characteristics such as strength, stress relaxation characteristics, and plating properties are improved without impairing electrical conductivity. The effect of addition is exhibited mainly by solid solution in the matrix. However, if the total amount of Sn and Zn exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, the Cu—Co—Si based alloy plate according to the present invention can be added with one or two selected from Sn and Zn up to a maximum of 2.0 mass% in total. However, if the amount is less than 0.05% by mass, the effect is small. Therefore, the total amount is preferably 0.05 to 2.0% by mass, and more preferably 0.5 to 1.0% by mass in total.
ｃ）Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｔｉ、Ｚｒ、Ａｌ及びＦｅの添加量
Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｔｉ、Ｚｒ、Ａｌ及びＦｅにおいても、要求される製品特性に応じて、添加量を調整することで、導電率、強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有され、若しくは新たな組成の第二相粒子を形成することで一層の効果を発揮させることもできる。しかしながら、これらの元素の総計が２．０質量％を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金板には、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｔｉ、Ｚｒ、Ａｌ及びＦｅから選択される１種又は２種以上を総計で最大２．０質量％添加することができる。但し、０．００１質量％未満ではその効果が小さいので、好ましくは総計で０．００１～２．０質量％、より好ましくは総計で０．０５～１．０質量％添加する。
上記したＭｇ、Ｐ、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｍｎ、Ｓｎ、Ｔｉ、Ｚｒ、Ａｌ、Ｆｅ、Ｚｎ及びＡｇの添加量が合計で２．０質量％を超えると製造性を損ないやすいので、好ましくはこれらの合計は２．０質量％以下とし、より好ましくは１．５質量％以下とし、更により好ましくは１．０質量％以下とする。 c) Addition amount of As, Sb, Be, B, Ti, Zr, Al, and Fe Also in As, Sb, Be, B, Ti, Zr, Al, and Fe, the addition amount is determined according to the required product characteristics. By adjusting, product characteristics such as conductivity, strength, stress relaxation characteristics, and plating properties are improved. The effect of addition is exhibited mainly by solid solution in the parent phase, but it can also be exhibited by forming the second phase particles having a new composition or contained in the second phase particles. However, if the total amount of these elements exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, in the Cu—Co—Si based alloy plate according to the present invention, the total amount of one or more selected from As, Sb, Be, B, Ti, Zr, Al and Fe is 2.0 mass in total. % Can be added. However, if the amount is less than 0.001% by mass, the effect is small. Therefore, the total amount is preferably 0.001 to 2.0% by mass, and more preferably 0.05 to 1.0% by mass.
If the total amount of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag exceeds 2.0% by mass, manufacturability is likely to be impaired. Preferably, the total of these is 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less.
Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｔｉ、Ｚｒ、Ａｌ及びＦｅにおいても、要求される製品特性に応じて、添加量を調整することで、導電率、強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有され、若しくは新たな組成の第二相粒子を形成することで一層の効果を発揮させることもできる。しかしながら、これらの元素の総計が２．０質量％を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るＣｕ－Ｃｏ－Ｓｉ系合金板には、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｔｉ、Ｚｒ、Ａｌ及びＦｅから選択される１種又は２種以上を総計で最大２．０質量％添加することができる。但し、０．００１質量％未満ではその効果が小さいので、好ましくは総計で０．００１～２．０質量％、より好ましくは総計で０．０５～１．０質量％添加する。
上記したＭｇ、Ｐ、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｍｎ、Ｓｎ、Ｔｉ、Ｚｒ、Ａｌ、Ｆｅ、Ｚｎ及びＡｇの添加量が合計で２．０質量％を超えると製造性を損ないやすいので、好ましくはこれらの合計は２．０質量％以下とし、より好ましくは１．５質量％以下とし、更により好ましくは１．０質量％以下とする。 c) Addition amount of As, Sb, Be, B, Ti, Zr, Al, and Fe Also in As, Sb, Be, B, Ti, Zr, Al, and Fe, the addition amount is determined according to the required product characteristics. By adjusting, product characteristics such as conductivity, strength, stress relaxation characteristics, and plating properties are improved. The effect of addition is exhibited mainly by solid solution in the parent phase, but it can also be exhibited by forming the second phase particles having a new composition or contained in the second phase particles. However, if the total amount of these elements exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, in the Cu—Co—Si based alloy plate according to the present invention, the total amount of one or more selected from As, Sb, Be, B, Ti, Zr, Al and Fe is 2.0 mass in total. % Can be added. However, if the amount is less than 0.001% by mass, the effect is small. Therefore, the total amount is preferably 0.001 to 2.0% by mass, and more preferably 0.05 to 1.0% by mass.
If the total amount of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag exceeds 2.0% by mass, manufacturability is likely to be impaired. Preferably, the total of these is 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less.
（４）結晶粒径
結晶粒径が小さいと高強度が得られることは従来から公知であり、本発明でも圧延方向断面の板厚中心の平均結晶粒径は２０μｍ以下である。ここで、板厚中心の平均結晶粒径は、ＪＩＳ Ｈ ０５０１（切断法）に基づき測定する。本発明の銅合金板の板厚中心の平均結晶粒径は、加工度１０～５０％の最終圧延の前後で著しい相対的変化は生じない。従って、最終圧延前で２０μｍ以下の平均結晶粒径であれば、平均結晶粒径２０μｍのサンプル銅合金よりも微細な結晶構造を、最終圧延後でも維持する。そのため、たとえ結晶構造が微細すぎて最終圧延後の平均結晶粒径が数値的に正確に測定できなくても、最終圧延前で平均結晶粒径２０μｍのサンプルを同一条件で最終圧延したものを標準として比較することにより、平均結晶粒径２０μｍを超えているかどうか判断できる。なお、本発明の「板厚中心で平均結晶粒径２０μｍ以下」は従来技術と同様の高強度を担保するための規定であり、「板厚中心」は測定位置を示すための文言である。 (4) Crystal grain size It has been heretofore known that high strength can be obtained when the crystal grain size is small. Even in the present invention, the average crystal grain size at the center of the thickness of the cross section in the rolling direction is 20 μm or less. Here, the average crystal grain size at the center of the plate thickness is measured based on JIS H 0501 (cutting method). The average crystal grain size at the center of the thickness of the copper alloy sheet of the present invention does not change significantly before and after the final rolling with a working degree of 10 to 50%. Therefore, if the average crystal grain size is 20 μm or less before the final rolling, a finer crystal structure than the sample copper alloy having an average crystal grain size of 20 μm is maintained even after the final rolling. Therefore, even if the crystal structure is too fine and the average crystal grain size after the final rolling cannot be measured numerically accurately, a sample obtained by final rolling a sample having an average crystal grain size of 20 μm under the same conditions before the final rolling is standard. It can be determined whether or not the average crystal grain size exceeds 20 μm. In the present invention, “the average crystal grain size of 20 μm or less at the center of the plate thickness” is a rule for ensuring the same high strength as in the prior art, and “the center of the plate thickness” is a word for indicating the measurement position.
結晶粒径が小さいと高強度が得られることは従来から公知であり、本発明でも圧延方向断面の板厚中心の平均結晶粒径は２０μｍ以下である。ここで、板厚中心の平均結晶粒径は、ＪＩＳ Ｈ ０５０１（切断法）に基づき測定する。本発明の銅合金板の板厚中心の平均結晶粒径は、加工度１０～５０％の最終圧延の前後で著しい相対的変化は生じない。従って、最終圧延前で２０μｍ以下の平均結晶粒径であれば、平均結晶粒径２０μｍのサンプル銅合金よりも微細な結晶構造を、最終圧延後でも維持する。そのため、たとえ結晶構造が微細すぎて最終圧延後の平均結晶粒径が数値的に正確に測定できなくても、最終圧延前で平均結晶粒径２０μｍのサンプルを同一条件で最終圧延したものを標準として比較することにより、平均結晶粒径２０μｍを超えているかどうか判断できる。なお、本発明の「板厚中心で平均結晶粒径２０μｍ以下」は従来技術と同様の高強度を担保するための規定であり、「板厚中心」は測定位置を示すための文言である。 (4) Crystal grain size It has been heretofore known that high strength can be obtained when the crystal grain size is small. Even in the present invention, the average crystal grain size at the center of the thickness of the cross section in the rolling direction is 20 μm or less. Here, the average crystal grain size at the center of the plate thickness is measured based on JIS H 0501 (cutting method). The average crystal grain size at the center of the thickness of the copper alloy sheet of the present invention does not change significantly before and after the final rolling with a working degree of 10 to 50%. Therefore, if the average crystal grain size is 20 μm or less before the final rolling, a finer crystal structure than the sample copper alloy having an average crystal grain size of 20 μm is maintained even after the final rolling. Therefore, even if the crystal structure is too fine and the average crystal grain size after the final rolling cannot be measured numerically accurately, a sample obtained by final rolling a sample having an average crystal grain size of 20 μm under the same conditions before the final rolling is standard. It can be determined whether or not the average crystal grain size exceeds 20 μm. In the present invention, “the average crystal grain size of 20 μm or less at the center of the plate thickness” is a rule for ensuring the same high strength as in the prior art, and “the center of the plate thickness” is a word for indicating the measurement position.
従来技術では、結晶粒径のばらつき、特に表面の粗大化結晶は特に着目されておらず、表面における粗大化結晶粒がめっきの均一付着性に悪影響を与えることは全く知られていなかった。しかし表層は、圧延工程で最も歪みエネルギーが溜まりやすく、通常の製造条件では内部（板厚中心）に比べて局部的に結晶が粗大化しやすい。また、熱処理工程においても表層と内部との熱履歴が異なる場合があり、内部（板厚中心）に比べて局部的に結晶が粗大化する場合もある。その場合、なお、ここでいう「表層」は表面から２５μｍの範囲をいう。
本発明者らは、Ｃｕ－Ｃｏ－Ｓｉ系合金板の表面の粗大化した結晶粒を少なくすることにより、めっきが均一に付着する電子材料用銅合金板が得られることを見いだした。
具体的には、表面に接した結晶粒でかつ最終圧延後の長径が４５μｍ以上の結晶粒が、圧延方向の長さ１ｍｍに対して５個以下、好ましくは４個以下、更に好ましくは２個以下であることである。５個を超えるとめっきが均一に付着せず、めっき表面を肉眼で見るとくもりが発生した状態の不良品となる。
また、結晶粒個数は、顕微鏡写真（倍率：×４００）において、圧延方向の断面の表面に接した４５μｍ以上の結晶粒の個数を測定し、複数（１０回）測定視野における表面の長さ２０００μｍの範囲の合計長さで結晶粒個数を割って１ｍｍ単位とした。 In the prior art, variations in crystal grain size, particularly coarse crystals on the surface, are not particularly noted, and it has not been known at all that coarse crystal grains on the surface adversely affect the uniform adhesion of plating. However, the surface layer is most likely to accumulate strain energy in the rolling process, and the crystals are likely to be locally coarsened in the normal manufacturing conditions as compared with the inside (center of the plate thickness). In the heat treatment process, the heat history may be different between the surface layer and the inside, and the crystal may be locally coarsened as compared with the inside (center of plate thickness). In this case, the “surface layer” here refers to a range of 25 μm from the surface.
The inventors of the present invention have found that a copper alloy plate for electronic materials to which plating is uniformly attached can be obtained by reducing the number of coarse crystal grains on the surface of the Cu—Co—Si alloy plate.
Specifically, the number of crystal grains in contact with the surface and having a major axis after final rolling of 45 μm or more is 5 or less, preferably 4 or less, more preferably 2 with respect to a length of 1 mm in the rolling direction. It is the following. When the number exceeds 5, the plating does not adhere uniformly, and when the surface of the plating is viewed with the naked eye, it becomes a defective product in a state where clouding occurs.
The number of crystal grains is determined by measuring the number of crystal grains of 45 μm or more in contact with the surface of the cross section in the rolling direction in a micrograph (magnification: × 400), and the length of the surface in multiple (10 times) measurement fields is 2000 μm. The number of crystal grains was divided by the total length in the range of 1 mm unit.
本発明者らは、Ｃｕ－Ｃｏ－Ｓｉ系合金板の表面の粗大化した結晶粒を少なくすることにより、めっきが均一に付着する電子材料用銅合金板が得られることを見いだした。
具体的には、表面に接した結晶粒でかつ最終圧延後の長径が４５μｍ以上の結晶粒が、圧延方向の長さ１ｍｍに対して５個以下、好ましくは４個以下、更に好ましくは２個以下であることである。５個を超えるとめっきが均一に付着せず、めっき表面を肉眼で見るとくもりが発生した状態の不良品となる。
また、結晶粒個数は、顕微鏡写真（倍率：×４００）において、圧延方向の断面の表面に接した４５μｍ以上の結晶粒の個数を測定し、複数（１０回）測定視野における表面の長さ２０００μｍの範囲の合計長さで結晶粒個数を割って１ｍｍ単位とした。 In the prior art, variations in crystal grain size, particularly coarse crystals on the surface, are not particularly noted, and it has not been known at all that coarse crystal grains on the surface adversely affect the uniform adhesion of plating. However, the surface layer is most likely to accumulate strain energy in the rolling process, and the crystals are likely to be locally coarsened in the normal manufacturing conditions as compared with the inside (center of the plate thickness). In the heat treatment process, the heat history may be different between the surface layer and the inside, and the crystal may be locally coarsened as compared with the inside (center of plate thickness). In this case, the “surface layer” here refers to a range of 25 μm from the surface.
The inventors of the present invention have found that a copper alloy plate for electronic materials to which plating is uniformly attached can be obtained by reducing the number of coarse crystal grains on the surface of the Cu—Co—Si alloy plate.
Specifically, the number of crystal grains in contact with the surface and having a major axis after final rolling of 45 μm or more is 5 or less, preferably 4 or less, more preferably 2 with respect to a length of 1 mm in the rolling direction. It is the following. When the number exceeds 5, the plating does not adhere uniformly, and when the surface of the plating is viewed with the naked eye, it becomes a defective product in a state where clouding occurs.
The number of crystal grains is determined by measuring the number of crystal grains of 45 μm or more in contact with the surface of the cross section in the rolling direction in a micrograph (magnification: × 400), and the length of the surface in multiple (10 times) measurement fields is 2000 μm. The number of crystal grains was divided by the total length in the range of 1 mm unit.
本発明の銅合金板は、表面に長径４５μｍ以上の結晶粒が５個以下であるため、めっきの均一付着性に優れる。本発明の銅合金板は、様々なめっき材料が適用でき、例えば、Ａｕめっきの下地に通常使用されるＮｉ下地めっきや、Ｃｕ下地めっき、Ｓｎめっきが挙げられる。
本発明のめっき厚みは、通常使用される２～５μｍの厚みはもとより、０．５～２．０μｍの厚みでも充分な均一付着性を示す。 Since the copper alloy plate of the present invention has 5 or less crystal grains having a major axis of 45 μm or more on the surface, it is excellent in uniform adhesion of plating. Various plating materials can be applied to the copper alloy plate of the present invention, and examples thereof include Ni base plating, Cu base plating, and Sn plating that are usually used for the base of Au plating.
The plating thickness of the present invention shows sufficient uniform adhesion even with a thickness of 0.5 to 2.0 μm as well as a thickness of 2 to 5 μm which is usually used.
本発明のめっき厚みは、通常使用される２～５μｍの厚みはもとより、０．５～２．０μｍの厚みでも充分な均一付着性を示す。 Since the copper alloy plate of the present invention has 5 or less crystal grains having a major axis of 45 μm or more on the surface, it is excellent in uniform adhesion of plating. Various plating materials can be applied to the copper alloy plate of the present invention, and examples thereof include Ni base plating, Cu base plating, and Sn plating that are usually used for the base of Au plating.
The plating thickness of the present invention shows sufficient uniform adhesion even with a thickness of 0.5 to 2.0 μm as well as a thickness of 2 to 5 μm which is usually used.
（５）製造方法
本発明の銅合金板の製造方法は、銅合金板で一般的な製造プロセス（溶解・鋳造→熱間圧延→中間冷間圧延→中間溶体化→最終冷間圧延→時効）を使用するが、その工程内で下記条件を調整して目的の銅合金板を製造する。なお、中間圧延、中間溶体化については、必要に応じて複数回くりかえしてもよい。
本発明では、熱間圧延、中間冷間圧延、中間溶体化処理の条件を厳密に制御することが重要である。その理由は、本発明の銅合金板には第二相粒子が粗大化しやすいＣｏが添加されており、第二相粒子の生成及び成長速度が、熱処理の際の保持温度と冷却速度に大きく影響されるためである。
溶解・鋳造工程では、電気銅、Ｓｉ、Ｃｏ等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後の、熱間圧延では均一な熱処理を行い、できる限り、鋳造で発生したＣｏ－Ｓｉ等の晶出物をなくす必要がある。例えば、９５０℃～１０５０℃で１時間以上保持後に熱間圧延を行う。熱間圧延前の保持温度が９５０℃未満では固溶が不充分であり、一方、１０５０℃を超えると材料が溶解する可能性がある。
また、熱間圧延終了時の温度が７００℃未満の場合には、熱間圧延の最終パス又は、最終パスを含む数パスの加工が７００℃未満で行われたことを意味する。熱間圧延終了時の温度が７００℃未満の場合には、内部は再結晶状態であるのに対して、表層は加工歪みを受けた状態で終了することとなる。この状態で冷間圧延を経て、通常の条件で溶体化を行われると、内部は正常な再結晶組織であるのに対して、表層は粗大化した結晶粒が形成されることとなる。そこで、表層の粗大化結晶の形成を防止するためには７００℃以上、好ましくは８５０℃以上で熱間圧延を終了することが望ましく、熱間圧延終了後は急冷することが望ましい。急冷は水冷により達成可能である。 (5) Manufacturing method The manufacturing method of the copper alloy plate of the present invention is a general manufacturing process using a copper alloy plate (melting / casting → hot rolling → intermediate cold rolling → intermediate solution forming → final cold rolling → aging). In this process, the following conditions are adjusted to produce the target copper alloy sheet. In addition, about intermediate rolling and intermediate solution forming, you may repeat several times as needed.
In the present invention, it is important to strictly control the conditions of hot rolling, intermediate cold rolling, and intermediate solution treatment. The reason for this is that the copper alloy plate of the present invention is added with Co, which tends to coarsen the second phase particles, and the generation and growth rate of the second phase particles greatly affects the holding temperature and cooling rate during the heat treatment. Because it is done.
In the melting / casting step, raw materials such as electrolytic copper, Si, and Co are melted to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. In the subsequent hot rolling, it is necessary to perform uniform heat treatment to eliminate crystallized substances such as Co—Si generated by casting as much as possible. For example, hot rolling is performed after holding at 950 ° C. to 1050 ° C. for 1 hour or longer. If the holding temperature before hot rolling is less than 950 ° C., solid solution is insufficient, while if it exceeds 1050 ° C., the material may be dissolved.
Moreover, when the temperature at the time of completion | finish of hot rolling is less than 700 degreeC, it means that the process of several passes including the last pass of a hot rolling or the last pass was performed at less than 700 degreeC. When the temperature at the end of hot rolling is less than 700 ° C., the inside is in a recrystallized state, whereas the surface layer is finished in a state where it is subjected to processing strain. In this state, when cold rolling is performed and solution treatment is performed under normal conditions, the inside is a normal recrystallized structure, whereas the surface layer is formed with coarse crystal grains. Therefore, in order to prevent the formation of coarse crystals on the surface layer, it is desirable to finish the hot rolling at 700 ° C. or higher, preferably 850 ° C. or higher, and to cool rapidly after the hot rolling is finished. Rapid cooling can be achieved by water cooling.
本発明の銅合金板の製造方法は、銅合金板で一般的な製造プロセス（溶解・鋳造→熱間圧延→中間冷間圧延→中間溶体化→最終冷間圧延→時効）を使用するが、その工程内で下記条件を調整して目的の銅合金板を製造する。なお、中間圧延、中間溶体化については、必要に応じて複数回くりかえしてもよい。
本発明では、熱間圧延、中間冷間圧延、中間溶体化処理の条件を厳密に制御することが重要である。その理由は、本発明の銅合金板には第二相粒子が粗大化しやすいＣｏが添加されており、第二相粒子の生成及び成長速度が、熱処理の際の保持温度と冷却速度に大きく影響されるためである。
溶解・鋳造工程では、電気銅、Ｓｉ、Ｃｏ等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後の、熱間圧延では均一な熱処理を行い、できる限り、鋳造で発生したＣｏ－Ｓｉ等の晶出物をなくす必要がある。例えば、９５０℃～１０５０℃で１時間以上保持後に熱間圧延を行う。熱間圧延前の保持温度が９５０℃未満では固溶が不充分であり、一方、１０５０℃を超えると材料が溶解する可能性がある。
また、熱間圧延終了時の温度が７００℃未満の場合には、熱間圧延の最終パス又は、最終パスを含む数パスの加工が７００℃未満で行われたことを意味する。熱間圧延終了時の温度が７００℃未満の場合には、内部は再結晶状態であるのに対して、表層は加工歪みを受けた状態で終了することとなる。この状態で冷間圧延を経て、通常の条件で溶体化を行われると、内部は正常な再結晶組織であるのに対して、表層は粗大化した結晶粒が形成されることとなる。そこで、表層の粗大化結晶の形成を防止するためには７００℃以上、好ましくは８５０℃以上で熱間圧延を終了することが望ましく、熱間圧延終了後は急冷することが望ましい。急冷は水冷により達成可能である。 (5) Manufacturing method The manufacturing method of the copper alloy plate of the present invention is a general manufacturing process using a copper alloy plate (melting / casting → hot rolling → intermediate cold rolling → intermediate solution forming → final cold rolling → aging). In this process, the following conditions are adjusted to produce the target copper alloy sheet. In addition, about intermediate rolling and intermediate solution forming, you may repeat several times as needed.
In the present invention, it is important to strictly control the conditions of hot rolling, intermediate cold rolling, and intermediate solution treatment. The reason for this is that the copper alloy plate of the present invention is added with Co, which tends to coarsen the second phase particles, and the generation and growth rate of the second phase particles greatly affects the holding temperature and cooling rate during the heat treatment. Because it is done.
In the melting / casting step, raw materials such as electrolytic copper, Si, and Co are melted to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. In the subsequent hot rolling, it is necessary to perform uniform heat treatment to eliminate crystallized substances such as Co—Si generated by casting as much as possible. For example, hot rolling is performed after holding at 950 ° C. to 1050 ° C. for 1 hour or longer. If the holding temperature before hot rolling is less than 950 ° C., solid solution is insufficient, while if it exceeds 1050 ° C., the material may be dissolved.
Moreover, when the temperature at the time of completion | finish of hot rolling is less than 700 degreeC, it means that the process of several passes including the last pass of a hot rolling or the last pass was performed at less than 700 degreeC. When the temperature at the end of hot rolling is less than 700 ° C., the inside is in a recrystallized state, whereas the surface layer is finished in a state where it is subjected to processing strain. In this state, when cold rolling is performed and solution treatment is performed under normal conditions, the inside is a normal recrystallized structure, whereas the surface layer is formed with coarse crystal grains. Therefore, in order to prevent the formation of coarse crystals on the surface layer, it is desirable to finish the hot rolling at 700 ° C. or higher, preferably 850 ° C. or higher, and to cool rapidly after the hot rolling is finished. Rapid cooling can be achieved by water cooling.
熱間圧延後には、中間圧延及び中間溶体化を目的の範囲内で回数及び順番を適宜選択して行う。中間圧延の最終パスの加工度が５％未満であると材料表面のみに加工歪エネルギーが蓄積されるため、表層に粗大な結晶粒が発生してしまう。特に最終パスの中間圧延加工度は、８％以上にすることが好ましい。また、中間圧延に使用される圧延油の粘度及び中間圧延の速度を制御することも均一に加工歪エネルギーを加えるのに有効である。
中間溶体化は、溶解鋳造時の晶出粒子や、熱延後の析出粒子を固溶させてできるかぎり粗大なＣｏ－Ｓｉ等の析出物をなくすために充分に行う。例えば、溶体化処理温度が８５０℃未満だと固溶が不充分であり、所望の強度を得ることが出来ない。一方、溶体化処理温度が１０５０℃を超えると材料が溶解する可能性がある。従って、材料温度を８５０℃～１０５０℃に加熱する溶体化処理を行うのが好ましい。溶体化処理の時間は０．５分～１時間とするのが好ましい。
なお、温度と時間の関係として、同じ熱処理効果（例えば、同じ結晶粒径）を得るため、常識的には、高温の場合には時間は短く、低温の場合には長くなければならない。例えば、本発明においては、９５０℃の場合には、１～２分、１０００℃の場合には０．５～１分が望ましい。
溶体化処理後の冷却速度は、一般的には固溶した第二相粒子の析出を防止するために急冷する。
続いて、時効処理を４００℃以上且つ６００℃以下の温度条件で行い、微細な第二相粒子を均一に析出させる。時効温度が４００℃未満であると、第二相粒子の析出が不十分であり、所望の強度と導電率を得ることができないという問題を有し、６００℃超であると析出した第二相粒子が粗大化してしまい、所望の強度を得ることができないという問題を有するためである。時効温度は、好ましくは４５０℃以上且つ５５０℃以下である。
最終圧延の加工度は好ましくは１０～５０％、好ましくは３０～５０％である。１０％未満であると所望の強度を得ることができない。一方、５０％を超えると曲げ加工性が劣化する。 After the hot rolling, intermediate rolling and intermediate solution forming are performed by appropriately selecting the number of times and the order within the target range. If the degree of processing in the final pass of the intermediate rolling is less than 5%, processing strain energy is accumulated only on the material surface, and coarse crystal grains are generated on the surface layer. In particular, the intermediate rolling degree of the final pass is preferably 8% or more. In addition, controlling the viscosity of the rolling oil used in the intermediate rolling and the speed of the intermediate rolling is also effective for uniformly applying the processing strain energy.
The intermediate solution treatment is carried out sufficiently to dissolve the crystallized particles at the time of melt casting and the precipitated particles after hot rolling so as to eliminate as coarse a Co—Si precipitate as possible. For example, if the solution treatment temperature is less than 850 ° C., the solid solution is insufficient and the desired strength cannot be obtained. On the other hand, when the solution treatment temperature exceeds 1050 ° C., the material may be dissolved. Therefore, it is preferable to perform a solution treatment in which the material temperature is heated to 850 ° C. to 1050 ° C. The solution treatment time is preferably 0.5 minutes to 1 hour.
It should be noted that, as a relationship between temperature and time, in order to obtain the same heat treatment effect (for example, the same crystal grain size), it is common knowledge that the time should be short at high temperatures and long at low temperatures. For example, in the present invention, 1 to 2 minutes is desirable at 950 ° C., and 0.5 to 1 minute is desirable at 1000 ° C.
The cooling rate after the solution treatment is generally quenched in order to prevent precipitation of solid solution second phase particles.
Subsequently, an aging treatment is performed under a temperature condition of 400 ° C. or more and 600 ° C. or less to precipitate fine second phase particles uniformly. If the aging temperature is less than 400 ° C., the second phase particles are not sufficiently precipitated, and the desired strength and electrical conductivity cannot be obtained. This is because the particles are coarsened and a desired strength cannot be obtained. The aging temperature is preferably 450 ° C. or higher and 550 ° C. or lower.
The degree of work of the final rolling is preferably 10 to 50%, preferably 30 to 50%. If it is less than 10%, the desired strength cannot be obtained. On the other hand, when it exceeds 50%, bending workability deteriorates.
中間溶体化は、溶解鋳造時の晶出粒子や、熱延後の析出粒子を固溶させてできるかぎり粗大なＣｏ－Ｓｉ等の析出物をなくすために充分に行う。例えば、溶体化処理温度が８５０℃未満だと固溶が不充分であり、所望の強度を得ることが出来ない。一方、溶体化処理温度が１０５０℃を超えると材料が溶解する可能性がある。従って、材料温度を８５０℃～１０５０℃に加熱する溶体化処理を行うのが好ましい。溶体化処理の時間は０．５分～１時間とするのが好ましい。
なお、温度と時間の関係として、同じ熱処理効果（例えば、同じ結晶粒径）を得るため、常識的には、高温の場合には時間は短く、低温の場合には長くなければならない。例えば、本発明においては、９５０℃の場合には、１～２分、１０００℃の場合には０．５～１分が望ましい。
溶体化処理後の冷却速度は、一般的には固溶した第二相粒子の析出を防止するために急冷する。
続いて、時効処理を４００℃以上且つ６００℃以下の温度条件で行い、微細な第二相粒子を均一に析出させる。時効温度が４００℃未満であると、第二相粒子の析出が不十分であり、所望の強度と導電率を得ることができないという問題を有し、６００℃超であると析出した第二相粒子が粗大化してしまい、所望の強度を得ることができないという問題を有するためである。時効温度は、好ましくは４５０℃以上且つ５５０℃以下である。
最終圧延の加工度は好ましくは１０～５０％、好ましくは３０～５０％である。１０％未満であると所望の強度を得ることができない。一方、５０％を超えると曲げ加工性が劣化する。 After the hot rolling, intermediate rolling and intermediate solution forming are performed by appropriately selecting the number of times and the order within the target range. If the degree of processing in the final pass of the intermediate rolling is less than 5%, processing strain energy is accumulated only on the material surface, and coarse crystal grains are generated on the surface layer. In particular, the intermediate rolling degree of the final pass is preferably 8% or more. In addition, controlling the viscosity of the rolling oil used in the intermediate rolling and the speed of the intermediate rolling is also effective for uniformly applying the processing strain energy.
The intermediate solution treatment is carried out sufficiently to dissolve the crystallized particles at the time of melt casting and the precipitated particles after hot rolling so as to eliminate as coarse a Co—Si precipitate as possible. For example, if the solution treatment temperature is less than 850 ° C., the solid solution is insufficient and the desired strength cannot be obtained. On the other hand, when the solution treatment temperature exceeds 1050 ° C., the material may be dissolved. Therefore, it is preferable to perform a solution treatment in which the material temperature is heated to 850 ° C. to 1050 ° C. The solution treatment time is preferably 0.5 minutes to 1 hour.
It should be noted that, as a relationship between temperature and time, in order to obtain the same heat treatment effect (for example, the same crystal grain size), it is common knowledge that the time should be short at high temperatures and long at low temperatures. For example, in the present invention, 1 to 2 minutes is desirable at 950 ° C., and 0.5 to 1 minute is desirable at 1000 ° C.
The cooling rate after the solution treatment is generally quenched in order to prevent precipitation of solid solution second phase particles.
Subsequently, an aging treatment is performed under a temperature condition of 400 ° C. or more and 600 ° C. or less to precipitate fine second phase particles uniformly. If the aging temperature is less than 400 ° C., the second phase particles are not sufficiently precipitated, and the desired strength and electrical conductivity cannot be obtained. This is because the particles are coarsened and a desired strength cannot be obtained. The aging temperature is preferably 450 ° C. or higher and 550 ° C. or lower.
The degree of work of the final rolling is preferably 10 to 50%, preferably 30 to 50%. If it is less than 10%, the desired strength cannot be obtained. On the other hand, when it exceeds 50%, bending workability deteriorates.
本発明の銅合金板は表面に粗大結晶粒子が存在しないため、めっきの均一付着性に優れ、リードフレーム、コネクタ、ピン、端子、リレー、スイッチ、二次電池用箔材等の電子部品に好適に使用できる。
Since the copper alloy plate of the present invention has no coarse crystal particles on the surface, it has excellent uniform plating adhesion, and is suitable for electronic parts such as lead frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries. Can be used for
以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。
（１）測定方法
（ａ）板厚中心の結晶粒径：溶体化処理後で最終圧延前の、圧延方向の板厚中心の平均結晶粒径２０μｍの標準サンプル（Ｃｏ：１．０質量％、Ｓｉ：０．６６質量％、残部銅）を製造した。平均結晶粒径は、ＪＩＳ Ｈ ０５０１（切断法）に基づき測定した。標準サンプルについて、最終冷間圧延（加工度１５％）を行い、圧延方向断面の板厚中心の光学顕微鏡写真（倍率：×４００）を撮影し、基準とした。そして各実施例（発明例及び比較例）の最終冷間圧延後の板厚中心の光学顕微鏡写真（基準と同倍率）と基準との大小を目視で比較し、大きい場合には２０μｍより大きく（＞２０μｍ）、同等か小さい場合には、２０μｍ以下（≦２０μｍ）とした。 Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
(1) Measurement method (a) Crystal grain size at the center of the plate thickness: Standard sample (Co: 1.0 mass%, average grain size of 20 μm at the center of the plate thickness in the rolling direction after the solution treatment and before final rolling Si: 0.66 mass%, balance copper) was produced. The average crystal grain size was measured based on JIS H 0501 (cutting method). The standard sample was subjected to final cold rolling (working degree 15%), and an optical micrograph (magnification: × 400) of the center of the thickness in the cross section in the rolling direction was taken as a reference. And the optical micrograph (same magnification as the standard) of the center of the thickness after the final cold rolling of each example (invention example and comparative example) and the size of the standard are visually compared, and if larger, larger than 20 μm ( > 20 μm), and when equal or smaller, 20 μm or less (≦ 20 μm).
（１）測定方法
（ａ）板厚中心の結晶粒径：溶体化処理後で最終圧延前の、圧延方向の板厚中心の平均結晶粒径２０μｍの標準サンプル（Ｃｏ：１．０質量％、Ｓｉ：０．６６質量％、残部銅）を製造した。平均結晶粒径は、ＪＩＳ Ｈ ０５０１（切断法）に基づき測定した。標準サンプルについて、最終冷間圧延（加工度１５％）を行い、圧延方向断面の板厚中心の光学顕微鏡写真（倍率：×４００）を撮影し、基準とした。そして各実施例（発明例及び比較例）の最終冷間圧延後の板厚中心の光学顕微鏡写真（基準と同倍率）と基準との大小を目視で比較し、大きい場合には２０μｍより大きく（＞２０μｍ）、同等か小さい場合には、２０μｍ以下（≦２０μｍ）とした。 Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
(1) Measurement method (a) Crystal grain size at the center of the plate thickness: Standard sample (Co: 1.0 mass%, average grain size of 20 μm at the center of the plate thickness in the rolling direction after the solution treatment and before final rolling Si: 0.66 mass%, balance copper) was produced. The average crystal grain size was measured based on JIS H 0501 (cutting method). The standard sample was subjected to final cold rolling (working degree 15%), and an optical micrograph (magnification: × 400) of the center of the thickness in the cross section in the rolling direction was taken as a reference. And the optical micrograph (same magnification as the standard) of the center of the thickness after the final cold rolling of each example (invention example and comparative example) and the size of the standard are visually compared, and if larger, larger than 20 μm ( > 20 μm), and when equal or smaller, 20 μm or less (≦ 20 μm).
（ｂ）表層近傍の結晶粒の観察
表層については、圧延方向表層断面の顕微鏡写真を使用し、表層から深さ１０μｍの位置に表面に平行な線を引き、線の長さを求めると同時に線分法によって、表面に一部でも接している４５μｍ以上の結晶粒径の個数を求めることを１０視野で行い、４５μｍ以上の結晶粒径の個数の合計を線分の合計で割って、１ｍｍ当たり４５μｍ以上の結晶粒径の個数を求めた。 (B) Observation of crystal grains in the vicinity of the surface layer For the surface layer, a micrograph of the surface layer cross section in the rolling direction is used, and a line parallel to the surface is drawn from the surface layer at a depth of 10 μm to obtain the length of the line. The number of crystal grain diameters of 45 μm or more that are partly in contact with the surface is obtained from the 10 fields of view by the division method, and the total number of crystal grain diameters of 45 μm or more is divided by the total of line segments to obtain per 1 mm The number of crystal grain sizes of 45 μm or more was determined.
表層については、圧延方向表層断面の顕微鏡写真を使用し、表層から深さ１０μｍの位置に表面に平行な線を引き、線の長さを求めると同時に線分法によって、表面に一部でも接している４５μｍ以上の結晶粒径の個数を求めることを１０視野で行い、４５μｍ以上の結晶粒径の個数の合計を線分の合計で割って、１ｍｍ当たり４５μｍ以上の結晶粒径の個数を求めた。 (B) Observation of crystal grains in the vicinity of the surface layer For the surface layer, a micrograph of the surface layer cross section in the rolling direction is used, and a line parallel to the surface is drawn from the surface layer at a depth of 10 μm to obtain the length of the line. The number of crystal grain diameters of 45 μm or more that are partly in contact with the surface is obtained from the 10 fields of view by the division method, and the total number of crystal grain diameters of 45 μm or more is divided by the total of line segments to obtain per 1 mm The number of crystal grain sizes of 45 μm or more was determined.
（ｃ）めっき付着の均一性
（電解脱脂手順）
アルカリ水溶液中で試料をカソードとして電解脱脂を行う。
１０質量％硫酸水溶液を用いて酸洗する。
（Ｎｉ下地めっき条件）
・めっき浴組成：硫酸ニッケル２５０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ／Ｌ
・めっき浴温度：５０℃
・電流密度：５Ａ／ｄｍ2
・Ｎｉめっき厚みは、電着時間により調整し、１．０μｍとした。めっき厚測定は、ＣＴ－１型電解式膜厚計（株式会社電測製）を用い、コクール社製電解液 Ｒ－５４を使用して行った。 (C) Uniformity of plating adhesion (electrolytic degreasing procedure)
Electrolytic degreasing is performed using a sample as a cathode in an alkaline aqueous solution.
Pickling is performed using a 10% by mass aqueous sulfuric acid solution.
(Ni base plating conditions)
-Plating bath composition: nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L
・ Plating bath temperature: 50 ℃
・ Current density: 5 A / dm 2
-Ni plating thickness was adjusted with the electrodeposition time, and was 1.0 micrometer. The plating thickness was measured using a CT-1 type electrolytic film thickness meter (manufactured by Denso Co., Ltd.) and an electrolytic solution R-54 manufactured by Kocourt.
（電解脱脂手順）
アルカリ水溶液中で試料をカソードとして電解脱脂を行う。
１０質量％硫酸水溶液を用いて酸洗する。
（Ｎｉ下地めっき条件）
・めっき浴組成：硫酸ニッケル２５０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ／Ｌ
・めっき浴温度：５０℃
・電流密度：５Ａ／ｄｍ2
・Ｎｉめっき厚みは、電着時間により調整し、１．０μｍとした。めっき厚測定は、ＣＴ－１型電解式膜厚計（株式会社電測製）を用い、コクール社製電解液 Ｒ－５４を使用して行った。 (C) Uniformity of plating adhesion (electrolytic degreasing procedure)
Electrolytic degreasing is performed using a sample as a cathode in an alkaline aqueous solution.
Pickling is performed using a 10% by mass aqueous sulfuric acid solution.
(Ni base plating conditions)
-Plating bath composition: nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L
・ Plating bath temperature: 50 ℃
・ Current density: 5 A / dm 2
-Ni plating thickness was adjusted with the electrodeposition time, and was 1.0 micrometer. The plating thickness was measured using a CT-1 type electrolytic film thickness meter (manufactured by Denso Co., Ltd.) and an electrolytic solution R-54 manufactured by Kocourt.
（めっき付着均一性評価）
めっき表面の光学顕微鏡写真（倍率：×２００、視野面積０．１ｍｍ2）を撮影し、島状めっきの個数及び分布状態を測定観察した。評価は下記の通りである。
Ｓ：なし、
Ａ：島状めっきの個数が５０個／ｍｍ2以下、
Ｂ：島状めっきの個数が１００個／ｍｍ2以下、
Ｃ：島状めっきの個数が１００個／ｍｍ2を超える。
なお、図１は、本発明例１のめっき表面の光学顕微鏡写真であり、「Ｓ」ランクに相当し、図２は、比較例１１のめっき表面の光学顕微鏡写真であり、「Ｃ」ランクに相当する。また、図３はめっき表面に観察される「島状めっき」の拡大写真（倍率：×２５００）であり、このような島形状を１個として視野中の島状めっきの個数を測定した。 (Evaluation of plating adhesion uniformity)
An optical micrograph of the plating surface (magnification: × 200, field of view area 0.1 mm 2 ) was taken, and the number and distribution of island-shaped plating were measured and observed. Evaluation is as follows.
S: None
A: The number of island-like plating is 50 / mm 2 or less,
B: The number of island-like plating is 100 pieces / mm 2 or less,
C: The number of island-shaped plating exceeds 100 pieces / mm 2 .
FIG. 1 is an optical micrograph of the plating surface of Example 1 of the present invention, which corresponds to “S” rank, and FIG. 2 is an optical micrograph of the plating surface of Comparative Example 11, and ranks “C”. Equivalent to. FIG. 3 is an enlarged photograph (magnification: × 2500) of “island-like plating” observed on the plating surface, and the number of island-like platings in the field of view was measured using such an island shape as one.
めっき表面の光学顕微鏡写真（倍率：×２００、視野面積０．１ｍｍ2）を撮影し、島状めっきの個数及び分布状態を測定観察した。評価は下記の通りである。
Ｓ：なし、
Ａ：島状めっきの個数が５０個／ｍｍ2以下、
Ｂ：島状めっきの個数が１００個／ｍｍ2以下、
Ｃ：島状めっきの個数が１００個／ｍｍ2を超える。
なお、図１は、本発明例１のめっき表面の光学顕微鏡写真であり、「Ｓ」ランクに相当し、図２は、比較例１１のめっき表面の光学顕微鏡写真であり、「Ｃ」ランクに相当する。また、図３はめっき表面に観察される「島状めっき」の拡大写真（倍率：×２５００）であり、このような島形状を１個として視野中の島状めっきの個数を測定した。 (Evaluation of plating adhesion uniformity)
An optical micrograph of the plating surface (magnification: × 200, field of view area 0.1 mm 2 ) was taken, and the number and distribution of island-shaped plating were measured and observed. Evaluation is as follows.
S: None
A: The number of island-like plating is 50 / mm 2 or less,
B: The number of island-like plating is 100 pieces / mm 2 or less,
C: The number of island-shaped plating exceeds 100 pieces / mm 2 .
FIG. 1 is an optical micrograph of the plating surface of Example 1 of the present invention, which corresponds to “S” rank, and FIG. 2 is an optical micrograph of the plating surface of Comparative Example 11, and ranks “C”. Equivalent to. FIG. 3 is an enlarged photograph (magnification: × 2500) of “island-like plating” observed on the plating surface, and the number of island-like platings in the field of view was measured using such an island shape as one.
（ｄ）強度
圧延平行方向の引っ張り試験を行って０．２％耐力（ＹＳ：ＭＰａ）を測定した。
（ｅ）導電率（ＥＣ；％ＩＡＣＳ）
ダブルブリッジによる体積抵抗率測定により求めた。
（ｆ）曲げ加工性
ＪＩＳ Ｈ ３１３０に従って、Ｂａｄｗａｙ（曲げ軸が圧延方向と同一方向）のＷ曲げ試験を行って、割れの発生しない最小半径（ＭＢＲ）の板厚（ｔ）に対する比であるＭＢＲ／ｔ値を測定した。曲げ加工性は以下の基準で評価した。
ＭＢＲ／ｔ≦２．０ 良好
２．０＜ＭＢＲ／ｔ 不良 (D) Strength A tensile test in the rolling parallel direction was performed to measure 0.2% yield strength (YS: MPa).
(E) Conductivity (EC;% IACS)
The volume resistivity was measured by a double bridge.
(F) Bending workability In accordance with JIS H 3130, a badway (bending axis is the same direction as the rolling direction) is subjected to a W-bending test, and MBR, which is a ratio of a minimum radius (MBR) to a thickness (t) at which no cracks occur. / T value was measured. Bending workability was evaluated according to the following criteria.
MBR / t ≦ 2.0 Good 2.0 <MBR / t Poor
圧延平行方向の引っ張り試験を行って０．２％耐力（ＹＳ：ＭＰａ）を測定した。
（ｅ）導電率（ＥＣ；％ＩＡＣＳ）
ダブルブリッジによる体積抵抗率測定により求めた。
（ｆ）曲げ加工性
ＪＩＳ Ｈ ３１３０に従って、Ｂａｄｗａｙ（曲げ軸が圧延方向と同一方向）のＷ曲げ試験を行って、割れの発生しない最小半径（ＭＢＲ）の板厚（ｔ）に対する比であるＭＢＲ／ｔ値を測定した。曲げ加工性は以下の基準で評価した。
ＭＢＲ／ｔ≦２．０ 良好
２．０＜ＭＢＲ／ｔ 不良 (D) Strength A tensile test in the rolling parallel direction was performed to measure 0.2% yield strength (YS: MPa).
(E) Conductivity (EC;% IACS)
The volume resistivity was measured by a double bridge.
(F) Bending workability In accordance with JIS H 3130, a badway (bending axis is the same direction as the rolling direction) is subjected to a W-bending test, and MBR, which is a ratio of a minimum radius (MBR) to a thickness (t) at which no cracks occur. / T value was measured. Bending workability was evaluated according to the following criteria.
MBR / t ≦ 2.0 Good 2.0 <MBR / t Poor
（２）製造方法
表１に記載の各成分組成の銅合金を、高周波溶解炉により１３００℃で溶製し、厚さ３０ｍｍのインゴットに鋳造した。次いで、このインゴットを表１に記載の条件で３時間加熱後、熱間圧延終了温度（上り温度）として板厚１０ｍｍまで熱間圧延し、熱間圧延終了後は速やかに室温まで水冷した。次いで、表面のスケール除去のため厚さ９ｍｍまで面削を施した後、最終パスの加工度５～１５％の冷間圧延、材料温度９００℃で０．５分～１時間の中間溶体化工程を適宜行い、厚さ０．１５ｍｍの板とした。溶体化処理終了後は速やかに室温まで水冷で冷却した。続いて、不活性雰囲気中、５２０℃で３時間の時効処理を行った。次いで、加工度１５％の最終冷間圧延を行い、各試験片を製造した。各試験片の測定結果を表１に示す。 (2) Manufacturing method The copper alloy of each component composition of Table 1 was melted at 1300 degreeC with the high frequency melting furnace, and it casted to the ingot of thickness 30mm. Next, this ingot was heated for 3 hours under the conditions shown in Table 1, and then hot-rolled to a plate thickness of 10 mm as the hot rolling end temperature (upward temperature). After the hot rolling was completed, it was rapidly cooled to room temperature. Next, after chamfering to a thickness of 9 mm to remove the scale from the surface, cold rolling with a final pass processing degree of 5 to 15%, intermediate solution treatment process at a material temperature of 900 ° C. for 0.5 minutes to 1 hour Was appropriately performed to obtain a plate having a thickness of 0.15 mm. After completion of the solution treatment, the solution was promptly cooled to room temperature by water cooling. Subsequently, an aging treatment was performed at 520 ° C. for 3 hours in an inert atmosphere. Subsequently, final cold rolling with a workability of 15% was performed to manufacture each test piece. Table 1 shows the measurement results of each test piece.
表１に記載の各成分組成の銅合金を、高周波溶解炉により１３００℃で溶製し、厚さ３０ｍｍのインゴットに鋳造した。次いで、このインゴットを表１に記載の条件で３時間加熱後、熱間圧延終了温度（上り温度）として板厚１０ｍｍまで熱間圧延し、熱間圧延終了後は速やかに室温まで水冷した。次いで、表面のスケール除去のため厚さ９ｍｍまで面削を施した後、最終パスの加工度５～１５％の冷間圧延、材料温度９００℃で０．５分～１時間の中間溶体化工程を適宜行い、厚さ０．１５ｍｍの板とした。溶体化処理終了後は速やかに室温まで水冷で冷却した。続いて、不活性雰囲気中、５２０℃で３時間の時効処理を行った。次いで、加工度１５％の最終冷間圧延を行い、各試験片を製造した。各試験片の測定結果を表１に示す。 (2) Manufacturing method The copper alloy of each component composition of Table 1 was melted at 1300 degreeC with the high frequency melting furnace, and it casted to the ingot of thickness 30mm. Next, this ingot was heated for 3 hours under the conditions shown in Table 1, and then hot-rolled to a plate thickness of 10 mm as the hot rolling end temperature (upward temperature). After the hot rolling was completed, it was rapidly cooled to room temperature. Next, after chamfering to a thickness of 9 mm to remove the scale from the surface, cold rolling with a final pass processing degree of 5 to 15%, intermediate solution treatment process at a material temperature of 900 ° C. for 0.5 minutes to 1 hour Was appropriately performed to obtain a plate having a thickness of 0.15 mm. After completion of the solution treatment, the solution was promptly cooled to room temperature by water cooling. Subsequently, an aging treatment was performed at 520 ° C. for 3 hours in an inert atmosphere. Subsequently, final cold rolling with a workability of 15% was performed to manufacture each test piece. Table 1 shows the measurement results of each test piece.
発明例１の最終パスにおける中間圧延の加工度１５％に対して、同一組成の発明例２では１０％と低いので表面に粗大粒子が発生してめっき均一付着性にやや劣る。発明例４と５の関係も同様である。
発明例１の上り温度（熱間圧延終了時の温度）７５０℃に対して、同一組成の発明例３では７００℃と低いので更にめっき均一付着性に劣る。発明例４と６の関係も同様である。
発明例１の熱間圧延スタート温度９５０℃、上り温度７５０℃に対して、同一組成の比較例１１では８００℃及び５００℃と低いので表面に粗大粒子が発生してめっき均一付着性に劣る。なお、比較例１１の銅合金表面にＮｉめっきを３．０μｍ厚みで施すと、めっき後の表面は、島状めっきは目立たなくなり、「Ｓ」ランクに近い状態となった。
発明例４と比較例１４の関係も同様である。 In contrast to the 15% workability of the intermediate rolling in the final pass of Invention Example 1, it is as low as 10% in Invention Example 2 having the same composition, so coarse particles are generated on the surface and the plating uniform adhesion is somewhat inferior. The relationship between Invention Examples 4 and 5 is the same.
Compared to 750 ° C. in the ascending temperature of Invention Example 1 (temperature at the end of hot rolling), 750 ° C. in Invention Example 3 having the same composition is further inferior in uniform plating adhesion. The relationship between Invention Examples 4 and 6 is the same.
In contrast to the hot rolling start temperature of 950 ° C. and ascending temperature of 750 ° C. in Invention Example 1, Comparative Example 11 having the same composition is as low as 800 ° C. and 500 ° C., so coarse particles are generated on the surface and the plating uniform adhesion is poor. In addition, when Ni plating was applied to the copper alloy surface of Comparative Example 11 with a thickness of 3.0 μm, the surface after plating was in a state close to the “S” rank because the island-like plating became inconspicuous.
The relationship between Invention Example 4 and Comparative Example 14 is the same.
発明例１の上り温度（熱間圧延終了時の温度）７５０℃に対して、同一組成の発明例３では７００℃と低いので更にめっき均一付着性に劣る。発明例４と６の関係も同様である。
発明例１の熱間圧延スタート温度９５０℃、上り温度７５０℃に対して、同一組成の比較例１１では８００℃及び５００℃と低いので表面に粗大粒子が発生してめっき均一付着性に劣る。なお、比較例１１の銅合金表面にＮｉめっきを３．０μｍ厚みで施すと、めっき後の表面は、島状めっきは目立たなくなり、「Ｓ」ランクに近い状態となった。
発明例４と比較例１４の関係も同様である。 In contrast to the 15% workability of the intermediate rolling in the final pass of Invention Example 1, it is as low as 10% in Invention Example 2 having the same composition, so coarse particles are generated on the surface and the plating uniform adhesion is somewhat inferior. The relationship between Invention Examples 4 and 5 is the same.
Compared to 750 ° C. in the ascending temperature of Invention Example 1 (temperature at the end of hot rolling), 750 ° C. in Invention Example 3 having the same composition is further inferior in uniform plating adhesion. The relationship between Invention Examples 4 and 6 is the same.
In contrast to the hot rolling start temperature of 950 ° C. and ascending temperature of 750 ° C. in Invention Example 1, Comparative Example 11 having the same composition is as low as 800 ° C. and 500 ° C., so coarse particles are generated on the surface and the plating uniform adhesion is poor. In addition, when Ni plating was applied to the copper alloy surface of Comparative Example 11 with a thickness of 3.0 μm, the surface after plating was in a state close to the “S” rank because the island-like plating became inconspicuous.
The relationship between Invention Example 4 and Comparative Example 14 is the same.
比較例１１の最終パスにおける中間圧延の加工度１５％に対して、同一組成の比較例１２では５％と低いので更に表面に粗大粒子が発生してめっき均一付着性劣る。
発明例７の熱間圧延スタート温度９５０℃、上り温度７５０℃、最終パスにおける中間圧延の加工度１５％に対して、同一組成の比較例１７では８００℃、５００℃、５％といずれも低いので表面に粗大粒子が発生してめっき均一付着性に劣る。発明例８と比較例１８の関係も同様である。 Compared to 15% of the degree of intermediate rolling in the final pass of Comparative Example 11, it is as low as 5% in Comparative Example 12 having the same composition, so that coarse particles are further generated on the surface, resulting in poor uniform plating adhesion.
The hot rolling start temperature of Invention Example 7 is 950 ° C., the ascending temperature is 750 ° C., and the processing degree of intermediate rolling in the final pass is 15%. Therefore, coarse particles are generated on the surface, resulting in poor uniform plating adhesion. The relationship between Invention Example 8 and Comparative Example 18 is the same.
発明例７の熱間圧延スタート温度９５０℃、上り温度７５０℃、最終パスにおける中間圧延の加工度１５％に対して、同一組成の比較例１７では８００℃、５００℃、５％といずれも低いので表面に粗大粒子が発生してめっき均一付着性に劣る。発明例８と比較例１８の関係も同様である。 Compared to 15% of the degree of intermediate rolling in the final pass of Comparative Example 11, it is as low as 5% in Comparative Example 12 having the same composition, so that coarse particles are further generated on the surface, resulting in poor uniform plating adhesion.
The hot rolling start temperature of Invention Example 7 is 950 ° C., the ascending temperature is 750 ° C., and the processing degree of intermediate rolling in the final pass is 15%. Therefore, coarse particles are generated on the surface, resulting in poor uniform plating adhesion. The relationship between Invention Example 8 and Comparative Example 18 is the same.
Claims (4)
- Ｃｏ：０．５～３．０質量％、Ｓｉ：０．１～１．０質量％を含有し、残部がＣｕ及び不可避不純物からなる電子材料用銅合金板であって、板厚中心の平均結晶粒径が２０μｍ以下で、表面に接した結晶粒でかつ長径が４５μｍ以上の結晶粒が、圧延方向長さ１ｍｍに対して５個以下であることを特徴とする電子材料用銅合金板。 Co: 0.5 to 3.0% by mass, Si: 0.1 to 1.0% by mass, the balance being a copper alloy plate for electronic materials consisting of Cu and inevitable impurities, the average of the thickness center A copper alloy sheet for electronic materials, wherein the crystal grain diameter is 20 μm or less, and the number of crystal grains in contact with the surface and having a major axis of 45 μm or more is 5 or less with respect to a length of 1 mm in the rolling direction.
- 更にＣｒを最大０．５質量％含有する請求項１記載の電子材料用銅合金板。 Furthermore, the copper alloy plate for electronic materials of Claim 1 which contains 0.5 mass% of Cr at the maximum.
- 更にＭｇ、Ｐ、Ａｓ、Ｓｂ、Ｂｅ、Ｂ、Ｍｎ、Ｓｎ、Ｔｉ、Ｚｒ、Ａｌ、Ｆｅ、Ｚｎ及びＡｇよりなる群から選ばれる１種又は２種以上を総計で最大２．０質量％含有する請求項１又は２記載の電子材料用銅合金板。 Furthermore, it contains at least 2.0% by mass in total of one or more selected from the group consisting of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag. The copper alloy plate for electronic materials according to claim 1 or 2.
- インゴットを溶解鋳造する工程と、
材料温度を９５０℃以上１０５０℃以下として１時間以上加熱後に、熱間圧延を行い、熱間圧延終了温度が７００℃以上である工程と、
最終パスが８％以上の加工度で行われる溶体化前の中間圧延工程と、
材料温度を８５０℃以上１０５０℃以下で０．５分～１時間加熱する中間溶体化工程と、
４００℃以上６００℃以下で加熱する時効工程と、
加工度１０～５０％の最終圧延工程と、
をこの順で行うことを含む請求項１～３いずれか１項記載の電子材料用銅合金板の製造方法。 Melting and casting the ingot;
A process in which the material temperature is set to 950 ° C. or higher and 1050 ° C. or lower and heated for 1 hour or longer, followed by hot rolling, and the hot rolling end temperature is 700 ° C. or higher;
An intermediate rolling step before solution treatment in which the final pass is performed at a working degree of 8% or more;
An intermediate solution forming step of heating at a material temperature of 850 ° C. to 1050 ° C. for 0.5 minutes to 1 hour;
An aging step of heating at 400 ° C. or higher and 600 ° C. or lower;
A final rolling step with a working degree of 10-50%,
The method for producing a copper alloy sheet for electronic materials according to any one of claims 1 to 3, comprising performing the steps in this order.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11789514.4A EP2578708A4 (en) | 2010-06-03 | 2011-03-24 | Cu-co-si-based alloy sheet, and process for production thereof |
| US13/581,715 US20130092297A1 (en) | 2010-06-03 | 2011-03-24 | Cu-Co-Si System Alloy Sheet and Method for Manufacturing Same |
| CN201180003593.1A CN102666890B (en) | 2010-06-03 | 2011-03-24 | Cu-Co-Si-based alloy sheet, and process for production thereof |
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| JP2010-127943 | 2010-06-03 | ||
| JP2010127943A JP4708497B1 (en) | 2010-06-03 | 2010-06-03 | Cu-Co-Si alloy plate and method for producing the same |
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| WO2011152104A1 true WO2011152104A1 (en) | 2011-12-08 |
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| US (1) | US20130092297A1 (en) |
| EP (1) | EP2578708A4 (en) |
| JP (1) | JP4708497B1 (en) |
| CN (1) | CN102666890B (en) |
| TW (1) | TWI422693B (en) |
| WO (1) | WO2011152104A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104342582A (en) * | 2013-07-31 | 2015-02-11 | Jx日矿日石金属株式会社 | Cu-Co-Si-based copper alloy strip and method of manufacturing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5437519B1 (en) | 2013-07-31 | 2014-03-12 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si-based copper alloy strip and method for producing the same |
| JP6294037B2 (en) * | 2013-09-18 | 2018-03-14 | 株式会社Maruwa | Composite noise filter |
| WO2015182786A1 (en) * | 2014-05-30 | 2015-12-03 | 古河電気工業株式会社 | Electric contact material, electric contact material manufacturing method, and terminal |
| JP6306632B2 (en) | 2016-03-31 | 2018-04-04 | Ｊｘ金属株式会社 | Copper alloy for electronic materials |
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| JP2005532477A (en) | 2002-07-05 | 2005-10-27 | オリン コーポレイション | Copper alloy containing cobalt, nickel and silicon |
| JP2007169765A (en) | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | Copper alloy and its production method |
| JP2008248333A (en) | 2007-03-30 | 2008-10-16 | Nikko Kinzoku Kk | Cu-Ni-Si-Co-BASED COPPER ALLOY FOR ELECTRONIC MATERIAL, AND MANUFACTURING METHOD THEREFOR |
| WO2010016428A1 (en) * | 2008-08-05 | 2010-02-11 | 古河電気工業株式会社 | Copper alloy material for electrical/electronic component |
| JP2010059543A (en) * | 2008-08-05 | 2010-03-18 | Furukawa Electric Co Ltd:The | Copper alloy material |
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| CN100439530C (en) * | 2004-12-24 | 2008-12-03 | 株式会社神户制钢所 | Copper alloy having bendability and stress relaxation property |
| WO2006101172A1 (en) * | 2005-03-24 | 2006-09-28 | Nippon Mining & Metals Co., Ltd. | Copper alloy for electronic material |
| JP5085908B2 (en) * | 2006-10-03 | 2012-11-28 | Ｊｘ日鉱日石金属株式会社 | Copper alloy for electronic materials and manufacturing method thereof |
| US20100326573A1 (en) * | 2008-01-30 | 2010-12-30 | Kuniteru Mihara | Copper alloy material for electric/electronic component and method for manufacturing the same |
| JP4596490B2 (en) * | 2008-03-31 | 2010-12-08 | Ｊｘ日鉱日石金属株式会社 | Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same |
| CN102112639A (en) * | 2008-07-31 | 2011-06-29 | 古河电气工业株式会社 | Copper alloy material for electrical and electronic components, and manufacturing method therefof |
| JP5261161B2 (en) * | 2008-12-12 | 2013-08-14 | Ｊｘ日鉱日石金属株式会社 | Ni-Si-Co-based copper alloy and method for producing the same |
-
2010
- 2010-06-03 JP JP2010127943A patent/JP4708497B1/en active Active
-
2011
- 2011-03-24 CN CN201180003593.1A patent/CN102666890B/en active Active
- 2011-03-24 WO PCT/JP2011/057216 patent/WO2011152104A1/en active Application Filing
- 2011-03-24 EP EP11789514.4A patent/EP2578708A4/en not_active Withdrawn
- 2011-03-24 US US13/581,715 patent/US20130092297A1/en not_active Abandoned
- 2011-04-18 TW TW100113320A patent/TWI422693B/en active
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| JP2005532477A (en) | 2002-07-05 | 2005-10-27 | オリン コーポレイション | Copper alloy containing cobalt, nickel and silicon |
| JP2007169765A (en) | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | Copper alloy and its production method |
| JP2008248333A (en) | 2007-03-30 | 2008-10-16 | Nikko Kinzoku Kk | Cu-Ni-Si-Co-BASED COPPER ALLOY FOR ELECTRONIC MATERIAL, AND MANUFACTURING METHOD THEREFOR |
| WO2010016428A1 (en) * | 2008-08-05 | 2010-02-11 | 古河電気工業株式会社 | Copper alloy material for electrical/electronic component |
| JP2010059543A (en) * | 2008-08-05 | 2010-03-18 | Furukawa Electric Co Ltd:The | Copper alloy material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104342582A (en) * | 2013-07-31 | 2015-02-11 | Jx日矿日石金属株式会社 | Cu-Co-Si-based copper alloy strip and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201200606A (en) | 2012-01-01 |
| CN102666890A (en) | 2012-09-12 |
| JP2011252216A (en) | 2011-12-15 |
| CN102666890B (en) | 2014-05-07 |
| JP4708497B1 (en) | 2011-06-22 |
| EP2578708A1 (en) | 2013-04-10 |
| US20130092297A1 (en) | 2013-04-18 |
| EP2578708A4 (en) | 2014-04-09 |
| TWI422693B (en) | 2014-01-11 |
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