TWI704240B - Copper alloy material for resistance material, manufacturing method thereof, and resistor - Google Patents
Copper alloy material for resistance material, manufacturing method thereof, and resistor Download PDFInfo
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Abstract
本發明提供一種電阻材料用銅合金材料及其製造方法，該電阻材料用銅合金材料兼具低電阻溫度係數與良好的沖壓成形性。其中，一種電阻材料用銅合金材料，其含有10質量%以上且14質量%以下的錳、1質量%以上且3質量%以下的鎳，剩餘部分由銅及無法避免的雜質所組成，並且，結晶粒徑是8微米以上且60微米以下。另一種電阻材料用銅合金材料，其含有6質量%以上且8質量%以下的錳、2質量%以上且4質量%以下的錫，剩餘部分由銅及無法避免的雜質所組成，並且，結晶粒徑是8微米以上且60微米以下。The invention provides a copper alloy material for resistance material and a manufacturing method thereof. The copper alloy material for resistance material has both low resistance temperature coefficient and good stamping formability. Among them, a copper alloy material for resistance materials contains 10% by mass or more and 14% by mass or less of manganese, 1% by mass or more and 3% by mass or less of nickel, and the remainder is composed of copper and unavoidable impurities, and, The crystal grain size is 8 microns or more and 60 microns or less. Another copper alloy material for resistance materials, which contains 6 mass% or more and 8 mass% or less of manganese, 2 mass% or more and 4 mass% or less of tin, the remainder is composed of copper and unavoidable impurities, and crystals The particle size is 8 microns or more and 60 microns or less.
Description
本發明關於電阻材料用銅合金材料及其製造方法、以及電阻器。The present invention relates to a copper alloy material for resistance material, a manufacturing method thereof, and a resistor.
就用於電阻器之電阻材料的金屬材料而言，要求電阻溫度係數（temperature coefficient of resistance，以下，也記載為「TCR」）要低，以使電阻器的電阻在環境溫度變化時仍然穩定。所謂電阻溫度係數，是將由於溫度造成的電阻值變化的大小以每1℃相應的百萬分率來呈現，並以TCR（×10-6 /K）=（R-R0 ）/R0 ×1/（T-T0 ）×106 的算式來呈現。此處，算式中的T表示試驗溫度（℃），T0 表示基準溫度（℃），R表示在試驗溫度T時的電阻值（Ω），R0 表示在試驗溫度T0 時的電阻值（Ω）。Cu-Mn-Ni合金和Cu-Mn-Sn合金，其TCR非常低，因此被廣泛用作為構成電阻材料之金屬材料（例如，參照專利文獻1）。 伴隨近年的電氣和電子零件的小型化和高集成化，電阻材料也進行著小型化。伴隨此小型化，將金屬材料作沖壓成形來製造電阻材料時的尺寸精度對於電阻器的電阻值偏差所帶來的影響也變大，於是尋求改善電阻材料的金屬材料的沖壓成形性。 [先前技術文獻] （專利文獻）Regarding the metal material used for the resistance material of the resistor, the temperature coefficient of resistance (hereinafter, also referred to as "TCR") is required to be low, so that the resistance of the resistor remains stable when the ambient temperature changes. The so-called temperature coefficient of resistance represents the change in resistance value due to temperature in parts per million per 1℃, and is expressed in terms of TCR (×10 -6 /K)=(RR 0 )/R 0 ×1 /(TT 0 )×10 6 expression. Here, T in the formula represents the test temperature (℃), T 0 represents the reference temperature (℃), R represents the resistance value (Ω) at the test temperature T, and R 0 represents the resistance value at the test temperature T 0 ( Ω). Cu-Mn-Ni alloys and Cu-Mn-Sn alloys have very low TCR, and therefore are widely used as metal materials constituting resistance materials (for example, refer to Patent Document 1). With the miniaturization and high integration of electrical and electronic parts in recent years, resistance materials have also been miniaturized. Along with this miniaturization, the dimensional accuracy when metal materials are press-formed to manufacture resistance materials has a greater influence on the resistance value deviation of resistors, and thus it is sought to improve the press-formability of metal materials of resistance materials. [Prior Art Document] (Patent Document)
專利文獻1：日本特許公開公報 2016年第69724號Patent Document 1: Japanese Patent Publication No. 69724, 2016
[發明所欲解決的問題] 本發明所欲解決的問題在於，提供一種電阻材料用銅合金材料及其製造方法，該電阻材料用銅合金材料兼具低電阻溫度係數與良好的沖壓成形性。又，本發明所欲解決的問題還在於提供一種電阻器，其即便環境溫度變化，該電阻器的電阻值仍然穩定，並且，電阻值偏差小。[Problem to be Solved by the Invention] The problem to be solved by the present invention is to provide a copper alloy material for resistance material and a manufacturing method thereof, which has a low temperature coefficient of resistance and good press formability. In addition, the problem to be solved by the present invention is to provide a resistor whose resistance value is stable even if the ambient temperature changes, and the resistance value deviation is small.
[用於解決問題的技術手段] 本發明的一態樣之電阻材料用銅合金材料，其重點在於：含有10質量%以上且14質量%以下的錳、1質量%以上且3質量%以下的鎳，剩餘部分由銅及無法避免的雜質所組成，並且，結晶粒徑是8微米（μm）以上且60μm以下。 本發明的另一態樣之電阻材料用銅合金材料，其重點在於：含有6質量%以上且8質量%以下的錳、2質量%以上且4質量%以下的錫，剩餘部分由銅及無法避免的雜質所組成，並且，結晶粒徑是8μm以上且60μm以下。[Technical Means for Solving the Problem] One aspect of the copper alloy material for resistance material of the present invention is that it contains 10% by mass or more and 14% by mass or less of manganese, and 1% by mass or more and 3% by mass or less. Nickel, the remainder is composed of copper and unavoidable impurities, and the crystal grain size is 8 microns (μm) or more and 60 μm or less. Another aspect of the copper alloy material for resistance materials of the present invention is that it contains 6 mass% or more and 8 mass% or less of manganese, 2 mass% or more and 4 mass% or less of tin, and the remainder is made of copper and cannot It is composed of avoidable impurities, and the crystal grain size is 8 μm or more and 60 μm or less.
本發明的另一態樣之電阻材料用銅合金材料的製造方法，其製造上述一態樣之電阻材料用銅合金材料或上述另一態樣之電阻材料用銅合金材料，該方法的重點在於具備：均質化熱處理步驟，其對銅合金的鑄塊（ingot）施行800℃以上且950℃以下並歷時10分鐘以上且10小時以下的熱處理；熱加工步驟，其對利用均質化熱處理步驟被均質化後的鑄塊施行熱加工；中間冷加工步驟，其對利用熱加工步驟施行熱加工後的鑄塊施行加工率50%以上的冷加工；中間再結晶退火步驟，其對利用中間冷加工步驟施行冷加工後的鑄塊施行400℃以上且700℃以下並歷時10秒以上且10小時以下的熱處理，以施行再結晶退火；最終冷加工步驟，其對利用中間再結晶退火步驟施行再結晶退火後的鑄塊施行加工率5%以上且80%以下的冷加工；以及，最終再結晶退火步驟，其對利用最終冷加工步驟施行冷加工後的鑄塊施行400℃以上且700℃以下並歷時10秒以上且10小時以下的熱處理，以施行再結晶退火。 本發明的另一態樣之電阻器，其重點在於：利用上述一態樣之電阻材料用銅合金材料或上述另一態樣之電阻材料用銅合金材料來構成至少一部分而成。A method of manufacturing a copper alloy material for resistance material in another aspect of the present invention, which manufactures the copper alloy material for resistance material of the above-mentioned aspect or the copper alloy material for resistance material of the above-mentioned another aspect, the focus of the method is Equipped with: a homogenization heat treatment step, which performs a heat treatment of 800°C or more and 950°C or less and lasts 10 minutes or more and 10 hours or less on the copper alloy ingot (ingot); a hot working step, which is homogenized by the homogenization heat treatment step Thermal processing is performed on the ingot after melting; an intermediate cold working step, which performs cold processing with a processing rate of more than 50% on the ingot after hot processing using the hot processing step; an intermediate recrystallization annealing step, which performs cold processing on the ingot after using the intermediate cold processing step The ingot is subjected to a heat treatment above 400°C and below 700°C for 10 seconds or more and 10 hours or less to perform recrystallization annealing; the final cold working step is performed on the ingot after the recrystallization annealing is performed using the intermediate recrystallization annealing step Cold working with a working rate of 5% or more and 80% or less; and, a final recrystallization annealing step, in which the ingot after being cold-worked by the final cold working step is subjected to 400°C or more and 700°C or less for 10 seconds or more and 10 hours or less Heat treatment to perform recrystallization annealing. The key point of another aspect of the resistor of the present invention is that at least a part of the above-mentioned one aspect of the resistance material is made of copper alloy material or the above-mentioned another aspect of the above-mentioned resistance material is made of copper alloy material.
[發明的功效] 本發明的電阻材料用銅合金材料，其兼具低電阻溫度係數與良好的沖壓成形性。 本發明的電阻材料用銅合金材料的製造方法，其能夠製造一種電阻材料用銅合金材料，該電阻材料用銅合金材料兼具低電阻溫度係數與良好的沖壓成形性。 本發明的電阻器，即便環境溫度變化，該電阻器的電阻值仍然穩定，並且，電阻值偏差小。[Effects of the invention] The copper alloy material for resistance material of the present invention has both a low temperature coefficient of resistance and good press formability. The method for manufacturing a copper alloy material for a resistance material of the present invention can produce a copper alloy material for a resistance material, which has a low temperature coefficient of resistance and good stamping formability. In the resistor of the present invention, even if the ambient temperature changes, the resistance value of the resistor is still stable, and the resistance value deviation is small.
針對本發明的一實施型態，詳細說明如下。 第一實施型態的電阻材料用銅合金材料，其含有10質量%以上且14質量%以下的錳（Mn）、1質量%以上且3質量%以下的鎳（Ni），剩餘部分由銅（Cu）及無法避免的雜質所組成，並且，結晶粒徑是8μm以上且60μm以下。此外，在本段落以後，也將第一實施型態的電阻材料用銅合金材料記載為「Cu-Mn-Ni合金材料」。A detailed description of one embodiment of the present invention is as follows. The copper alloy material for resistance materials of the first embodiment contains 10% by mass or more and 14% by mass or less of manganese (Mn), 1% by mass or more and 3% by mass or less of nickel (Ni), and the remainder is made of copper ( Cu) and unavoidable impurities, and the crystal grain size is 8 μm or more and 60 μm or less. In addition, after this paragraph, the copper alloy material for the resistance material of the first embodiment is also described as "Cu-Mn-Ni alloy material".
第二實施型態的電阻材料用銅合金材料，其含有6質量%以上且8質量%以下的錳、2質量%以上且4質量%以下的錫（Sn），剩餘部分由銅及無法避免的雜質所組成，並且，結晶粒徑是8μm以上且60μm以下。此外，在本段落以後，也將第二實施型態的電阻材料用銅合金材料記載為「Cu-Mn-Sn合金材料」。The copper alloy material for the resistance material of the second embodiment contains 6 mass% or more and 8 mass% or less of manganese, 2 mass% or more and 4 mass% or less of tin (Sn), and the remainder is made of copper and unavoidable It is composed of impurities, and the crystal grain size is 8 μm or more and 60 μm or less. In addition, after this paragraph, the copper alloy material for the resistance material of the second embodiment is also described as "Cu-Mn-Sn alloy material".
這些第一及第二實施型態的電阻材料用銅合金材料，其結晶粒徑被控制在8μm以上且60μm以下，因此兼具低電阻溫度係數與良好的沖壓成形性。因此，第一及第二實施型態的電阻材料用銅合金材料，其適合作為構成電阻材料之金屬材料，該電阻材料被使用於例如分路電阻器（shunt resistor）等電阻器。These copper alloy materials for resistance materials of the first and second embodiments have a crystal grain size of 8 μm or more and 60 μm or less, and therefore have both a low temperature coefficient of resistance and good press formability. Therefore, the copper alloy material for the resistance material of the first and second embodiments is suitable as a metal material constituting the resistance material, and the resistance material is used in resistors such as shunt resistors.
第一及第二實施型態的電阻材料用銅合金材料，其由於電阻溫度係數低，故即便環境溫度變化，該電阻器的電阻值仍然穩定。關於第一及第二實施型態的電阻材料用銅合金材料的電阻溫度係數，在20℃以上且50℃以下的範圍內，電阻溫度係數的絕對值可以是50ppm/K以下。若電阻溫度係數是上述範圍內，則在環境溫度變化時，電阻值的穩定性較良好。The copper alloy material for the resistance material of the first and second embodiments has a low resistance temperature coefficient, so even if the ambient temperature changes, the resistance value of the resistor remains stable. Regarding the temperature coefficient of resistance of the copper alloy material for resistance materials of the first and second embodiments, the absolute value of the temperature coefficient of resistance may be 50 ppm/K or less in the range of 20° C. or more and 50° C. or less. If the temperature coefficient of resistance is within the above range, the stability of the resistance value will be better when the ambient temperature changes.
又，第一及第二實施型態的電阻材料用銅合金材料，其由於沖壓成形性良好，故在將銅合金材料沖壓成形來製造電阻材料時，即便電阻材料是小型，尺寸精度也優良。關於第一及第二實施型態的電阻材料用銅合金材料的沖壓成形性，其能夠以剪切比作為指標。例如，若根據日本伸銅協會技術標準JCBA T310：2002規定的銅及銅合金薄板條的剪切試驗方法所測得的剪切比是未滿85%，則沖壓成形性會較優良，於是在沖壓成形時的尺寸精度會較優良。In addition, the copper alloy materials for resistance materials of the first and second embodiments have good press formability. Therefore, when the copper alloy material is press-formed to produce a resistance material, even if the resistance material is small, the dimensional accuracy is excellent. Regarding the press formability of the copper alloy materials for resistance materials of the first and second embodiments, the shear ratio can be used as an index. For example, if the shear ratio measured by the shear test method of copper and copper alloy thin strips according to the technical standard JCBA T310: 2002 of the Japan Copper Wire Association is less than 85%, the stamping formability will be better, so the The dimensional accuracy during press forming will be better.
此外，第一及第二實施型態的電阻材料用銅合金材料，其不只是沖壓成形性，在其他加工方法中的成形性也優良。 第一及第二實施型態的電阻材料用銅合金材料，其具有如上所述的優良特性，因此，利用第一及第二實施型態的電阻材料用銅合金材料來構成至少一部分而成的電阻器，即便環境溫度變化，該電阻器的電阻值仍然穩定，並且，電阻值偏差小。In addition, the copper alloy materials for resistance materials of the first and second embodiments are not only press formability, but also excellent formability in other processing methods. The copper alloy material for the resistance material of the first and second embodiments has excellent characteristics as described above. Therefore, the copper alloy material for the resistance material of the first and second embodiments is used to form at least a part In the resistor, even if the ambient temperature changes, the resistance value of the resistor is still stable, and the resistance value deviation is small.
第一實施型態的電阻材料用銅合金材料，其含有10質量%以上且14質量%以下的錳、1質量%以上且3質量%以下的鎳，若錳的含量未滿10質量%，則會有TCR變大之虞，並且，再結晶退火時，結晶粒徑會容易變大。另一方面，若錳的含量超過14質量%，則會有電阻率變高之虞，並且，再結晶退火時，結晶粒徑會容易變小。進一步，會有電阻材料用銅合金材料的耐蝕性與製造性下降之虞。The copper alloy material for the resistance material of the first embodiment contains 10% by mass or more and 14% by mass or less of manganese and 1% by mass or more and 3% by mass or less of nickel. If the manganese content is less than 10% by mass, There is a possibility that the TCR may become larger, and the crystal grain size may easily become larger during recrystallization annealing. On the other hand, if the content of manganese exceeds 14% by mass, the electrical resistivity may increase, and the crystal grain size may easily decrease during recrystallization annealing. Furthermore, there is a possibility that the corrosion resistance and manufacturability of the copper alloy material for resistance materials may decrease.
又，若鎳的含量未滿1質量%，則會有TCR變大之虞，並且，再結晶退火時，結晶粒徑會容易變大。進一步，會有電阻材料用銅合金材料的耐蝕性下降之虞。另一方面，若鎳的含量超過3質量%，則會有電阻率變高之虞，並且，再結晶退火時，結晶粒徑會容易變小。進一步，會有電阻材料用銅合金材料的製造性下降之虞。In addition, if the nickel content is less than 1% by mass, the TCR may increase, and the crystal grain size may easily increase during recrystallization annealing. Furthermore, there is a possibility that the corrosion resistance of the copper alloy material for resistance material may decrease. On the other hand, if the content of nickel exceeds 3% by mass, the electrical resistivity may increase, and the crystal grain size may easily decrease during recrystallization annealing. Furthermore, there is a possibility that the manufacturability of the copper alloy material for resistance material may decrease.
第二實施型態的電阻材料用銅合金材料，其含有6質量%以上且8質量%以下的錳、2質量%以上且4質量%以下的錫，若錳的含量未滿6質量%，則會有TCR變大之虞，並且，再結晶退火時，結晶粒徑會容易變大。另一方面，若錳的含量超過8質量%，則會有電阻率變高之虞，並且，再結晶退火時，結晶粒徑會容易變小。The copper alloy material for resistance materials of the second embodiment contains 6 mass% or more and 8 mass% or less of manganese, 2 mass% or more and 4 mass% or less of tin. If the manganese content is less than 6 mass%, There is a possibility that the TCR may become larger, and the crystal grain size may easily become larger during recrystallization annealing. On the other hand, if the content of manganese exceeds 8% by mass, the electrical resistivity may increase, and the crystal grain size may easily decrease during recrystallization annealing.
又，若錫的含量未滿2質量%，則會有TCR變大之虞，並且，再結晶退火時，結晶粒徑會容易變大。進一步，會有電阻材料用銅合金材料的耐蝕性下降之虞。另一方面，若錫的含量超過4質量%，則會有電阻率變高之虞，並且，再結晶退火時，結晶粒徑會容易變小。進一步，會有電阻材料用銅合金材料的製造性下降之虞。Moreover, if the content of tin is less than 2% by mass, the TCR may increase, and the crystal grain size may easily increase during recrystallization annealing. Furthermore, there is a possibility that the corrosion resistance of the copper alloy material for resistance material may decrease. On the other hand, if the content of tin exceeds 4% by mass, the electrical resistivity may increase, and the crystal grain size may easily decrease during recrystallization annealing. Furthermore, there is a possibility that the manufacturability of the copper alloy material for resistance material may decrease.
第一實施型態的電阻材料用銅合金材料，其可進一步含有錳、鎳以外的合金成分。又，第二實施型態的電阻材料用銅合金材料，其可進一步含有錳、錫以外的合金成分。在任一實施型態的電阻材料用銅合金材料中，可含有的合金成分是：選自由0.001質量%以上且0.5質量%以下的鐵（Fe）、0.001質量%以上且0.1質量%以下的矽（Si）、0.001質量%以上且0.5質量%以下的鉻（Cr）、0.001質量%以上且0.2質量%以下的鋯（Zr）、0.001質量%以上且0.2質量%以下的鈦（Ti）、0.001質量%以上且0.5質量%以下的銀（Ag）、0.001質量%以上且0.5質量%以下的鎂（Mg）、0.001質量%以上且0.1質量%以下的鈷（Co）、0.001質量%以上且0.1質量%以下的磷（P）、以及0.001質量%以上且0.5質量%以下的鋅（Zn）所組成之群組的1種或2種以上的元素。The copper alloy material for the resistance material of the first embodiment may further contain alloy components other than manganese and nickel. In addition, the copper alloy material for a resistance material of the second embodiment may further contain alloy components other than manganese and tin. In any embodiment of the copper alloy material for resistance material, the alloy components that can be contained are: iron (Fe) selected from 0.001 mass% to 0.5 mass%, 0.001 mass% to 0.1 mass% silicon ( Si), 0.001 mass% or more and 0.5 mass% or less chromium (Cr), 0.001 mass% or more and 0.2 mass% or less zirconium (Zr), 0.001 mass% or more and 0.2 mass% or less titanium (Ti), 0.001 mass% % Or more and 0.5% by mass or less of silver (Ag), 0.001% by mass or more and 0.5% by mass or less of magnesium (Mg), 0.001% by mass or more and 0.1% by mass or less of cobalt (Co), 0.001% by mass or more and 0.1% by mass One or two or more elements of the group consisting of phosphorus (P) in an amount of 0.001% by mass or more and 0.5% by mass or less of zinc (Zn).
藉由含有這些合金成分，電阻材料用銅合金材料的耐熱性會提升，並且，再結晶退火時，晶粒成長會變慢，因此結晶粒徑的控制會變成較容易。若這些合金成分的含量超過上述範圍的上限值，則會有抑制晶粒成長的作用變得過大之虞。又，會有電阻率變高之虞，並且，會有電阻材料用銅合金材料的製造性下降之虞。By containing these alloy components, the heat resistance of the copper alloy material for the resistance material is improved, and the crystal grain growth becomes slower during the recrystallization annealing, so the control of the crystal grain size becomes easier. If the content of these alloy components exceeds the upper limit of the above-mentioned range, the effect of suppressing the growth of crystal grains may become excessive. In addition, the resistivity may increase, and the manufacturability of the copper alloy material for resistance material may decrease.
第一實施型態的電阻材料用銅合金材料，其藉由將結晶粒徑作成在前述範圍內，並且，在後述的最終再結晶退火步驟以後不進行冷加工，能夠使維氏硬度（Vickers hardness）成為90HV以上且未滿150HV，進一步較佳是成為90HV以上且135HV以下。若第一實施型態的電阻材料用銅合金材料的維氏硬度未滿90HV，則結晶粒徑會超出並大於前述範圍，而會有沖壓成形性變得不足的情況。另一方面，若維氏硬度是150HV以上，則意謂結晶粒徑超出並小於前述範圍、或在最終再結晶退火步驟以後施行了冷加工，於是會有無法獲得低電阻溫度係數的情況。The copper alloy material for the resistance material of the first embodiment can achieve Vickers hardness by setting the crystal grain size within the aforementioned range and not performing cold working after the final recrystallization annealing step described later. It is 90 HV or more and less than 150 HV, more preferably 90 HV or more and 135 HV or less. If the Vickers hardness of the copper alloy material for the resistance material of the first embodiment is less than 90 HV, the crystal grain size will exceed and exceed the aforementioned range, and the press formability may become insufficient. On the other hand, if the Vickers hardness is 150HV or more, it means that the crystal grain size exceeds and is smaller than the aforementioned range, or cold working is performed after the final recrystallization annealing step, and thus a low temperature coefficient of resistance cannot be obtained.
第二實施型態的電阻材料用銅合金材料，其藉由將結晶粒徑作成在前述範圍內，並且，在後述的最終再結晶退火步驟以後不進行冷加工，能夠使維氏硬度成為80HV以上且未滿120HV，進一步較佳是成為90HV以上且105HV以下。若第二實施型態的電阻材料用銅合金材料的維氏硬度未滿80HV，則結晶粒徑會超出並大於前述範圍，而會有沖壓成形性變得不足的情況。另一方面，若維氏硬度是120HV以上，則意謂結晶粒徑超出並小於前述範圍、或在最終再結晶退火步驟以後施行了冷加工，於是會有無法獲得低電阻溫度係數的情況。The second embodiment of the copper alloy material for resistance materials can make the Vickers hardness 80HV or more by making the crystal grain size within the aforementioned range and without cold working after the final recrystallization annealing step described later. It is less than 120HV, and more preferably 90HV or more and 105HV or less. If the Vickers hardness of the copper alloy material for resistance material of the second embodiment is less than 80 HV, the crystal grain size will exceed and exceed the aforementioned range, and the press formability may become insufficient. On the other hand, if the Vickers hardness is 120HV or more, it means that the crystal grain size exceeds and is smaller than the aforementioned range, or cold working is performed after the final recrystallization annealing step, and thus a low temperature coefficient of resistance cannot be obtained.
隨後，針對第一及第二實施型態的電阻材料用銅合金材料的製造方法來作說明。第一及第二實施型態的電阻材料用銅合金材料，其能夠藉由同樣的方法來製造。亦即，一種方法，其具備：均質化熱處理步驟，其對銅合金的鑄塊施行800℃以上且950℃以下並歷時10分鐘以上且10小時以下的熱處理；熱加工步驟，其對利用均質化熱處理步驟被均質化後的鑄塊施行熱加工；中間冷加工步驟，其對利用熱加工步驟施行熱加工後的鑄塊施行加工率50%以上的冷加工；中間再結晶退火步驟，其對利用中間冷加工步驟施行冷加工後的鑄塊施行400℃以上且700℃以下並歷時10秒以上且10小時以下的熱處理，以施行再結晶退火；最終冷加工步驟，其對利用中間再結晶退火步驟施行再結晶退火後的鑄塊施行加工率5%以上且80%以下的冷加工；以及，最終再結晶退火步驟，其對利用最終冷加工步驟施行冷加工後的鑄塊施行400℃以上且700℃以下並歷時10秒以上且10小時以下的熱處理，以施行再結晶退火。Subsequently, the method of manufacturing the copper alloy material for the resistance material of the first and second embodiments will be described. The copper alloy material used as the resistance material of the first and second embodiments can be manufactured by the same method. That is, a method comprising: a homogenization heat treatment step of subjecting a copper alloy ingot to a heat treatment of 800° C. or more and 950° C. and a duration of 10 minutes or more and 10 hours or less; a thermal processing step that uses homogenization The ingot after the heat treatment step is homogenized is subjected to hot working; the intermediate cold working step is to perform cold working with a processing rate of more than 50% on the ingot after hot working by the hot working step; the intermediate recrystallization annealing step is to use intermediate cold working The ingot after the cold working step is subjected to a heat treatment at 400°C or higher and 700°C or higher and lasts for 10 seconds or more and 10 hours or less to perform recrystallization annealing; the final cold working step is to perform recrystallization annealing on the intermediate recrystallization annealing step The ingot is subjected to cold working with a processing rate of 5% or more and 80% or less; and the final recrystallization annealing step, which performs the cold working of the ingot by the final cold working step on the ingot after being cold-worked at 400°C or higher and 700°C or lower for 10 seconds or more and Heat treatment for less than 10 hours to perform recrystallization annealing.
藉由這種製造方法，能夠製造第一及第二實施型態的電阻材料用銅合金材料，其結晶粒徑是8μm以上且60μm以下。第一及第二實施型態的電阻材料用銅合金材料，其可成形為任何形狀的部件，例如，可成形為線材、棒材、板材等。以下，作為一個例子，說明利用第一及第二實施型態的電阻材料用銅合金材料構成之板材的製造方法。With this manufacturing method, it is possible to manufacture the copper alloy materials for resistance materials of the first and second embodiments, the crystal grain size of which is 8 μm or more and 60 μm or less. The copper alloy materials for resistance materials of the first and second embodiments can be formed into parts of any shape, for example, they can be formed into wires, rods, plates, and the like. Hereinafter, as an example, a method for manufacturing a plate made of a copper alloy material for a resistance material of the first and second embodiments will be described.
首先，使用爐等來熔解原料（raw material）後加以鑄造，而獲得具有上述合金成分之鑄塊（鑄造步驟）。隨後，將利用鑄造步驟所獲得的鑄塊作熱處理來使合金成分均質化（均質化熱處理步驟）。均質化熱處理步驟中的熱處理條件，其可依據合金組成來適當設定，不過，作為一個例子，能夠舉出在800℃以上且950℃以下並歷時10分鐘以上且10小時以下之條件。若加熱溫度過高、加熱時間過長之類的話，會有電阻材料用銅合金材料的加工性下降之虞。另一方面，若加熱溫度過低、加熱時間過短之類的話，則會有合金成分的均質化變得不足之虞。First, a furnace or the like is used to melt the raw material and then cast to obtain an ingot having the above alloy composition (casting step). Subsequently, the ingot obtained by the casting step is heat-treated to homogenize the alloy composition (homogenization heat treatment step). The heat treatment conditions in the homogenization heat treatment step can be appropriately set according to the alloy composition. However, as an example, a condition of at least 800° C. and not more than 950° C for 10 minutes or more and 10 hours or less can be mentioned. If the heating temperature is too high or the heating time is too long, the workability of the copper alloy material for resistance material may decrease. On the other hand, if the heating temperature is too low or the heating time is too short, the homogenization of alloy components may become insufficient.
隨後，對藉由均質化熱處理步驟被均質化後的鑄塊施行熱加工，將鑄塊成形為所需形狀的部件（熱加工步驟）。例如，將鑄塊作熱軋延而成形為呈約略板狀的板狀物。由於均質化熱處理步驟剛結束後的鑄塊是加熱至高溫的狀態，故較佳是就此連續地移送至熱加工步驟來實施熱加工。若熱加工結束，則將板狀物冷卻至常溫。由於在熱加工步驟後的板狀物的表面形成有氧化皮膜，故將此氧化皮膜去除（表面磨削步驟）。Subsequently, hot working is performed on the ingot homogenized by the homogenization heat treatment step, and the ingot is formed into a part of a desired shape (hot working step). For example, the ingot is hot rolled and formed into a plate-like shape having an approximately plate shape. Since the ingot immediately after the homogenization heat treatment step is heated to a high temperature, it is preferable to continuously transfer it to the hot working step to perform the hot working. When the thermal processing is completed, the plate-like object is cooled to normal temperature. Since an oxide film is formed on the surface of the plate after the thermal processing step, this oxide film is removed (surface grinding step).
隨後，對已去除氧化皮膜的板狀物施行加工率50%以上的冷加工（中間冷加工步驟）。例如，將板狀物作冷軋延來將板厚加以薄化。若加工率是50%以上，則能夠將直到熱加工步驟為止所獲得的材料組織充分地微細化，因此最終所獲得的結晶粒徑不會變得過大，而容易成為適當的大小。Subsequently, cold working (intermediate cold working step) with a processing rate of 50% or more is performed on the plate-like object from which the oxide film has been removed. For example, cold rolling a plate to thin the plate thickness. If the processing rate is 50% or more, the material structure obtained up to the hot working step can be sufficiently refined. Therefore, the crystal grain size finally obtained does not become too large, and it is easy to become an appropriate size.
隨後，對利用中間冷加工步驟施行冷加工來將板厚加以薄化後的板狀物作熱處理，以施行再結晶退火（中間再結晶退火步驟）。中間再結晶退火步驟中的熱處理條件，其可依據合金組成等來適當設定，但作為一個例子，能夠舉出在400℃以上且700℃以下並歷時10秒以上且10小時以下之條件。若加熱溫度過高、加熱時間過長之類的話，則會有無法將直到熱加工步驟為止所獲得的材料組織充分地微細化而無法減小最終所獲得的結晶粒徑之虞。另一方面，若加熱溫度過低、加熱時間過短之類的話，則會有無法獲得再結晶組織、或是再結晶組織變得過小而最終所獲得的結晶粒徑變小之虞。就此熱處理而言，可使用將板狀物放入爐內後加以升溫之批次熱處理，也可使用使板狀物連續地通過已升溫的爐內之移動式（traveling）熱處理。Subsequently, the plate-like object whose plate thickness is thinned by cold working in an intermediate cold working step is heat-treated to perform recrystallization annealing (intermediate recrystallization annealing step). The heat treatment conditions in the intermediate recrystallization annealing step can be appropriately set depending on the alloy composition, etc. However, as an example, a condition of 400° C. or more and 700° C. for 10 seconds or more and 10 hours or less can be mentioned. If the heating temperature is too high or the heating time is too long, the material structure obtained up to the thermal processing step may not be sufficiently refined and the crystal grain size finally obtained may not be reduced. On the other hand, if the heating temperature is too low or the heating time is too short, the recrystallized structure may not be obtained, or the recrystallized structure may become too small, and the finally obtained crystal grain size may become small. For this heat treatment, a batch heat treatment in which the plate is placed in a furnace and then heated, can also be used, and a traveling heat treatment in which the plate is continuously passed through a heated furnace can also be used.
隨後，對利用中間再結晶退火步驟施行再結晶退火後的板狀物施行加工率5%以上且80%以下的冷加工（最終冷加工步驟）。例如，將板狀物作冷軋延來將板厚進一步加以薄化以作成所需的厚度。若加工率超過80%，則會有最終所獲得的結晶粒徑變小之虞。另一方面，若加工率未滿5%，則會有無法獲得再結晶組織、或是最終所獲得的結晶粒徑變大之虞。Subsequently, the plate after the recrystallization annealing is performed in the intermediate recrystallization annealing step is subjected to cold working with a working rate of 5% or more and 80% or less (final cold working step). For example, cold-rolling a plate-shaped object can further reduce the plate thickness to a desired thickness. If the processing rate exceeds 80%, the crystal grain size finally obtained may become smaller. On the other hand, if the processing rate is less than 5%, the recrystallized structure may not be obtained, or the crystal grain size finally obtained may become large.
隨後，將利用最終冷加工步驟施行冷加工來將板厚進一步加以薄化後的板狀物作熱處理，以施行再結晶退火（最終再結晶退火步驟）。最終再結晶退火步驟中的熱處理條件，其可依據合金組成等來適當設定，但作為一個例子，能夠舉出在400℃以上且700℃以下並歷時10秒以上且10小時以下之條件。若加熱溫度過高、加熱時間過長之類的話，則會有最終所獲得的結晶粒徑變大之虞。另一方面，若加熱溫度過低、加熱時間過短之類的話，則會有無法獲得再結晶組織、或是最終所獲得的結晶粒徑變小之虞。就此熱處理而言，可使用將板狀物放入爐內後加以升溫之批次熱處理，也可使用使板狀物連續地通過已升溫的爐內之移動式熱處理。Subsequently, the plate-like object whose plate thickness is further thinned by cold working in the final cold working step is heat-treated to perform recrystallization annealing (final recrystallization annealing step). The heat treatment conditions in the final recrystallization annealing step can be appropriately set depending on the alloy composition, etc. However, as an example, a condition of 400° C. or more and 700° C. for 10 seconds or more and 10 hours or less can be mentioned. If the heating temperature is too high, the heating time is too long, etc., the crystal grain size finally obtained may become larger. On the other hand, if the heating temperature is too low and the heating time is too short, there is a possibility that the recrystallized structure cannot be obtained or the crystal grain size finally obtained becomes small. For this heat treatment, a batch heat treatment in which a plate is placed in a furnace and then heated up can be used, or a mobile heat treatment in which a plate is continuously passed through a heated furnace.
藉由具備如上所述的步驟之製造方法，能夠製造一種利用第一及第二實施型態的電阻材料用銅合金材料構成之板材，其結晶粒徑是8μm以上且60μm以下。進一步，依據製造方法和條件，能夠將結晶粒徑作成8μm以上且45μm以下，也能夠作成8μm以上且25μm以下。藉由中間冷加工步驟與中間再結晶退火步驟，來將直到熱加工步驟為止所獲得的材料組織充分地微細化，並藉由最終冷加工步驟與最終再結晶退火步驟，來獲得所需的結晶粒徑。不過，上述中間冷加工步驟與中間再結晶退火步驟，可以各進行一次，也可以在進行最終冷加工步驟前各自重複進行複數次。With the manufacturing method including the steps described above, it is possible to manufacture a plate made of the copper alloy material for the resistance material of the first and second embodiments, the crystal grain size of which is 8 μm or more and 60 μm or less. Furthermore, depending on the manufacturing method and conditions, the crystal grain size can be 8 μm or more and 45 μm or less, and it can also be 8 μm or more and 25 μm or less. Through the intermediate cold working step and the intermediate recrystallization annealing step, the material structure obtained up to the hot working step is sufficiently refined, and the final cold working step and the final recrystallization annealing step are used to obtain the desired crystal grain size . However, the intermediate cold working step and the intermediate recrystallization annealing step may be performed once each, or they may be repeated multiple times before the final cold working step.
又，在相鄰的步驟與步驟之間、或在最終再結晶退火步驟後，可實施矯正形狀、去除氧化膜、脫脂、防鏽等處理。不過，若在最終再結晶退火步驟後進行任何步驟，則在該加工是低度變形(low deformation)的情況下，會有變得組織不均勻而無法獲得穩定的TCR之虞，在該加工是高度變形(high deformation)的情況下，會有硬度增加而致操作變得困難之虞。因此，較佳是在最終再結晶退火步驟後，不進行任何加工。In addition, between adjacent steps and steps, or after the final recrystallization annealing step, treatments such as shape correction, oxide film removal, degreasing, and rust prevention may be performed. However, if any step is performed after the final recrystallization annealing step, if the processing is low deformation, the structure may become uneven and stable TCR may not be obtained. In the case of high deformation, the hardness may increase and the operation may become difficult. Therefore, it is preferable not to perform any processing after the final recrystallization annealing step.
並且，本實施型態顯示本發明的一個例子，本發明並非僅限於本實施形態。又，可對本實施型態加入各種變更或改良，此加入多樣變更或改良後的型態亦可包含於本發明中。 [實施例]In addition, this embodiment mode shows an example of the present invention, and the present invention is not limited to this embodiment. In addition, various changes or improvements can be added to this embodiment, and various changes or improvements can also be included in the present invention. [Example]
以下，顯示實施例及比較例來進一步具體說明本發明。藉由鑄造來製造具有預定的合金組成之鑄塊，並利用加熱溫度800℃以上且950℃以下並歷時加熱時間10分鐘以上且10小時以下之條件來熱處理來將合金成分作均質化後，藉由熱軋延成形為板狀並進行水冷。Hereinafter, examples and comparative examples are shown to further specifically illustrate the present invention. An ingot with a predetermined alloy composition is produced by casting, and the heating temperature is 800°C or higher and 950°C or lower, and the heating time is 10 minutes or more and 10 hours or less. It is formed into a plate shape by hot rolling and water-cooled.
隨後，在對藉由熱軋延所獲得的板狀物施行表面磨削來去除表面的氧化皮膜後，以預定的加工率來將板狀物作冷軋延（中間冷加工步驟），進一步接著以預定的條件（加熱溫度及加熱時間）作熱處理，以施行再結晶退火（中間再結晶退火步驟）。進一步，以預定的加工率來將板狀物作冷軋延（最終冷加工步驟），進一步接著以預定的條件（加熱溫度及加熱時間）作熱處理，以施行再結晶退火（最終再結晶退火步驟），而獲得厚度0.2mm的板材。Subsequently, after surface grinding is performed on the plate obtained by hot rolling to remove the oxide film on the surface, the plate is cold rolled at a predetermined processing rate (intermediate cold working step), and further followed by The predetermined conditions (heating temperature and heating time) are heat treated to perform recrystallization annealing (intermediate recrystallization annealing step). Furthermore, the plate is cold rolled at a predetermined processing rate (final cold working step), and then subjected to heat treatment under predetermined conditions (heating temperature and heating time) to perform recrystallization annealing (final recrystallization annealing step) , And obtain a thickness of 0.2mm plate.
合金組成如表1～4所示，表1～4所示的合金成分以外的剩餘部分是銅及無法避免的雜質。又，中間冷加工步驟、中間再結晶退火步驟、最終冷加工步驟、以及最終再結晶退火步驟的各條件，如表1～4所示。表1是將合金組成作各種變更後的Cu-Mn-Ni合金材料的例子，表2是將合金組成作各種變更後的Cu-Mn-Sn合金材料的例子。又，表3是將上述四個步驟的條件作各種變更後的Cu-Mn-Ni合金材料的例子，表4是將上述四個步驟的條件作各種變更後的Cu-Mn-Sn合金材料的例子。並且，相較於表3、4的製造條件，表1、2的製造條件更佳。The alloy composition is shown in Tables 1 to 4, and the remainder other than the alloy composition shown in Tables 1 to 4 is copper and unavoidable impurities. In addition, the conditions of the intermediate cold working step, the intermediate recrystallization annealing step, the final cold working step, and the final recrystallization annealing step are shown in Tables 1 to 4. Table 1 is an example of Cu-Mn-Ni alloy material after various changes of alloy composition, and Table 2 is an example of Cu-Mn-Sn alloy material after various changes of alloy composition. In addition, Table 3 is an example of Cu-Mn-Ni alloy materials with various changes in the conditions of the above four steps, and Table 4 is a Cu-Mn-Sn alloy material with various changes in the conditions of the above four steps example. In addition, the manufacturing conditions of Tables 1 and 2 are better than those of Tables 3 and 4.
［表1］
［表2］
［表3］
［表4］
針對表1～4所示的實施例1～36及比較例1～36的板材，進行各種評估。以下，說明其內容與方法。又，評估結果顯示於表5～8中。 ＜關於結晶粒徑的測定＞ 根據JIS H0501（1986）規定的伸銅品(將銅進行軋延加工而得的製品)結晶粒度試驗方法的切斷法，進行了結晶粒徑的測定。亦即，將板材沿著軋延方向作切斷而露出剖面後，對該剖面施行濕式鏡面研磨。然後，蝕刻該研磨面後，使用金相顯微鏡（metallurgical microscope）來觀察，並由觀察到的圖像來測定結晶粒徑。Various evaluations were performed on the plates of Examples 1 to 36 and Comparative Examples 1 to 36 shown in Tables 1 to 4. The content and method are explained below. In addition, the evaluation results are shown in Tables 5-8. <About the measurement of crystal grain size> The measurement of the crystal grain size was carried out in accordance with the cutting method of the crystal grain size test method for copper elongated products (products obtained by rolling copper) specified in JIS H0501 (1986). That is, after the sheet material is cut along the rolling direction to expose the cross section, the cross section is subjected to wet mirror polishing. Then, after etching the polished surface, it is observed with a metallurgical microscope, and the crystal grain size is measured from the observed image.
＜關於X射線繞射＞ 對板材的表面，進行θ-2θ法的X射線繞射，檢測出(111)、(200)、(220)、(311)、(222)、(400)、(331)、(420)的峰，並評估其體積比與半值寬度。並且，入射X射線的種類是Cu-Kα，燈管電壓是40kV，燈管電流是20mA，取樣速度是1°/min。<About X-ray diffraction> The X-ray diffraction of the θ-2θ method was performed on the surface of the plate, and (111), (200), (220), (311), (222), (400), ( 331) and (420) peaks, and evaluate their volume ratio and half-value width. In addition, the type of incident X-ray is Cu-Kα, the lamp voltage is 40kV, the lamp current is 20mA, and the sampling speed is 1°/min.
＜關於電阻溫度係數的測定＞ 根據JIS C2526(1994)規定的方法，測定了板材的20℃以上且50℃以下之範圍內的電阻溫度係數。將20℃以上且50℃以下之範圍內的電阻溫度係數的絕對值是50ppm/K以下的情況設為合格，並在表5～8中以「○」符號顯示。將20℃以上且50℃以下之範圍內的電阻溫度係數的絕對值超過50ppm/K的情況設為不合格，並在表5～8中以「×」符號顯示。<About the measurement of the temperature coefficient of resistance> According to the method specified in JIS C2526 (1994), the temperature coefficient of resistance of the sheet material in the range of 20°C or more and 50°C or less was measured. The case where the absolute value of the temperature coefficient of resistance in the range of 20°C or higher and 50°C or lower is 50 ppm/K or lower is regarded as acceptable, and is indicated by the "○" symbol in Tables 5 to 8. If the absolute value of the temperature coefficient of resistance in the range of 20°C or higher and 50°C or lower exceeds 50 ppm/K, it is regarded as unacceptable, and it is shown as "×" in Tables 5 to 8.
＜關於沖壓成形性＞ 藉由根據日本伸銅協會技術標準JCBA T310：2002規定的銅及銅合金薄板條的剪切試驗方法所測得的剪切比，來評估板材的沖壓成形性。亦即，使用沖壓機、矩形模具切塊（dice）等來將板材作沖孔，露出垂直於板材的軋延方向的剖面（沖壓破斷面）後，使用掃描式電子顯微鏡來進行剖面觀察，並算出剪切比。並且，關於板材沖孔中的條件，間隔（clearance）是10μm，沖壓速度是200mm/s，潤滑條件是無潤滑。 在剪切比未滿85%的情況下，評估為沖壓成形性優良，在表5～8中以「○」符號顯示。在剪切比是85%以上的情況下，評估為沖壓成形性不足，在表5～8中以「×」符號顯示。<About stamping formability> The stamping formability of the sheet is evaluated by the shear ratio measured according to the shear test method of copper and copper alloy thin strips specified in the technical standard JCBA T310: 2002 of the Japan Copper Wire Association. That is, a punching machine, rectangular die dice, etc. are used to punch the plate to expose a section perpendicular to the rolling direction of the plate (punching fracture surface), and then use a scanning electron microscope to observe the section. And calculate the shear ratio. In addition, regarding the conditions in the sheet punching, the clearance is 10 μm, the punching speed is 200 mm/s, and the lubrication condition is no lubrication. In the case where the shear ratio is less than 85%, it is evaluated that the press formability is excellent, and it is indicated by "○" in Tables 5 to 8. When the shear ratio is 85% or more, it is evaluated that the press formability is insufficient, and it is indicated by the symbol "×" in Tables 5 to 8.
＜關於維氏硬度的測定＞ 根據JIS Z2244(2009)規定的方法，由板材的表面來測定維氏硬度。並且，荷重是2.9N，壓頭（indenter）的壓下時間是15秒。<About the measurement of Vickers hardness> According to the method specified in JIS Z2244 (2009), the Vickers hardness was measured from the surface of the sheet material. In addition, the load is 2.9N, and the depressing time of the indenter is 15 seconds.
由表5～8所示的結果可知，實施例1～36的板材，其結晶粒徑是8μm以上且60μm以下，因此兼具低電阻溫度係數與良好的沖壓成形性。 相較於此，比較例1～8是合金組成超出本發明的合適範圍的例子，比較例1～7的板材，其合金組成超出本發明的合適範圍，因此結晶粒徑成為未滿8μm或超過60μm，而無法兼具低電阻溫度係數與良好的沖壓成形性。又，比較例1與比較例4，其Mn的含量低，因此即使結晶粒徑是在規定的範圍內，也無法獲得低電阻溫度係數。From the results shown in Tables 5 to 8, it can be seen that the plates of Examples 1 to 36 have a crystal grain size of 8 μm or more and 60 μm or less, and therefore have a low temperature coefficient of resistance and good press formability. In contrast, Comparative Examples 1 to 8 are examples in which the alloy composition exceeds the appropriate range of the present invention. The plates of Comparative Examples 1 to 7 have alloy compositions beyond the appropriate range of the present invention, so the crystal grain size becomes less than 8 μm or exceeds 60μm, and cannot have both low resistance temperature coefficient and good stamping formability. In addition, since Comparative Example 1 and Comparative Example 4 have a low Mn content, even if the crystal grain size is within a predetermined range, a low temperature coefficient of resistance cannot be obtained.
比較例8，其合金組成超出本發明的合適範圍，因此在熱軋延時，板狀物中會產生破裂，而無法進行至之後的步驟來獲得板材。 比較例9～44，其是製造條件超出本發明的合適範圍的例子，比較例9～14、17～23、26～32、35～41及44的板材，其製造條件超出本發明的合適範圍，因此結晶粒徑成為未滿8μm或超過60μm，而無法兼具低電阻溫度係數與良好的沖壓成形性。 比較例15、16、24、25、33、34、42、43的板材，其製造條件超出本發明的合適範圍，因此無法藉由最終再結晶退火步驟來獲得再結晶組織，而無法兼具低電阻溫度係數與良好的沖壓成形性。In Comparative Example 8, the alloy composition is out of the suitable range of the present invention. Therefore, when the hot rolling is delayed, cracks will occur in the plate, and it is impossible to proceed to the subsequent steps to obtain the plate. Comparative Examples 9 to 44 are examples where the manufacturing conditions are outside the suitable range of the present invention. The plates of Comparative Examples 9 to 14, 17 to 23, 26 to 32, 35 to 41 and 44 are manufactured under conditions outside the suitable range of the present invention Therefore, the crystal grain size becomes less than 8 μm or more than 60 μm, and it is impossible to have both low temperature coefficient of resistance and good press formability. The plates of Comparative Examples 15, 16, 24, 25, 33, 34, 42, and 43 have manufacturing conditions outside of the appropriate range of the present invention. Therefore, the final recrystallization annealing step cannot be used to obtain a recrystallized structure, and it cannot have both low Temperature coefficient of resistance and good stamping formability.
［表5］
［表6］
［表7］
［表8］
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| CN103060605B (en) * | 2013-01-16 | 2015-06-03 | 苏州金仓合金新材料有限公司 | Novel lead-free environmentally-friendly high-strength wearable copper-based alloy rod and preparation method thereof |
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| JP2017002407A (en) | 2016-08-23 | 2017-01-05 | Ｊｘ金属株式会社 | Copper alloy sheet excellent in conductivity and stress relaxation characteristic |
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2017
- 2017-12-13 JP JP2018524299A patent/JP6382478B1/en active Active
- 2017-12-13 CN CN202210509500.2A patent/CN114959355A/en active Pending
- 2017-12-13 WO PCT/JP2017/044779 patent/WO2018131373A1/en active Application Filing
- 2017-12-13 KR KR1020197018158A patent/KR102463644B1/en active IP Right Grant
- 2017-12-13 CN CN201780082526.0A patent/CN110168120A/en active Pending
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711455A (en) * | 2013-12-16 | 2015-06-17 | 深南电路有限公司 | Film resistor material, film resistor and preparation method of film resistor |
| TW201612327A (en) * | 2014-09-29 | 2016-04-01 | Hitachi Metals Ltd | Copper alloy material and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110168120A (en) | 2019-08-23 |
| KR102463644B1 (en) | 2022-11-07 |
| TW201835344A (en) | 2018-10-01 |
| JPWO2018131373A1 (en) | 2019-01-24 |
| JP6382478B1 (en) | 2018-08-29 |
| CN114959355A (en) | 2022-08-30 |
| KR20190105574A (en) | 2019-09-17 |
| WO2018131373A1 (en) | 2018-07-19 |
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