JP2016180131A - Cu-Ni-Si-BASED COPPER ALLOY SHEET MATERIAL AND METHOD FOR PRODUCING THE SAME, AND LEAD FRAME - Google Patents
Cu-Ni-Si-BASED COPPER ALLOY SHEET MATERIAL AND METHOD FOR PRODUCING THE SAME, AND LEAD FRAME Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 62
- 238000012360 testing method Methods 0.000 claims abstract description 43
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- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
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- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
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- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 4
- 238000005097 cold rolling Methods 0.000 claims description 36
- 238000000137 annealing Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 28
- 230000035882 stress Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
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Abstract
Description
本発明は、高強度、高導電性、および低熱収縮性を有するCu−Ni−Si系銅合金板材、およびその製造方法に関する。また、その銅合金板材を用いたリードフレームに関する。 The present invention relates to a Cu—Ni—Si based copper alloy sheet having high strength, high conductivity, and low heat shrinkability, and a method for producing the same. The present invention also relates to a lead frame using the copper alloy sheet.
電気・電子部品を構成する通電部品に用いる素材(板材)には、基本的特性として「強度」および「導電性」に優れることが要求される。さらに、リードフレーム等の精密部品に加工する素材には、当該部品に加工したときに良好な形状(すなわち高い寸法精度)が得られる性質を具備していることが要求される。 A material (plate material) used for an energized component constituting an electric / electronic component is required to have excellent “strength” and “conductivity” as basic characteristics. Furthermore, a material to be processed into a precision part such as a lead frame is required to have a property that a good shape (that is, high dimensional accuracy) can be obtained when processed into the part.
ところが、一般に、銅合金板材において高強度化を図ろうとすると、精密部品に加工する際の寸法精度を良好に維持することが難しくなる。最近では半導体パッケージの小型・薄型化が進み、リードフレームの外周リード部分(アウターリード)を取り除いたQFN(Quad Flat Non−Leaded Package)と呼ばれるパッケージが多用されるようになり、しかも多ピン化のニーズが高まっている。QFNタイプの多ピン化に対応するためには、従来にも増して高強度化と寸法精度の向上を高レベルで実現しうる素材が要求される。 However, in general, when trying to increase the strength of a copper alloy sheet, it is difficult to maintain good dimensional accuracy when processing into a precision part. Recently, semiconductor packages have become smaller and thinner, and a package called QFN (Quad Flat Non-Leaded Package) in which the outer peripheral lead portion (outer lead) of the lead frame has been removed has been used frequently. Needs are growing. In order to cope with the increase in the number of pins of the QFN type, a material capable of realizing higher strength and improved dimensional accuracy at a higher level than before is required.
強度と導電性の特性バランスに優れた銅合金として、Cu−Ni−Si系銅合金(いわゆるコルソン合金)がある。この合金系では比較的高い導電率(35〜50%IACS)を維持しながら0.2%耐力800MPa以上の高強度に調整することができる。特許文献1には熱収縮を改善した高強度Cu−Ni−Si系銅合金が記載されている。特許文献2〜5には内部残留応力を低減した高強度Cu−Ni−Si系銅合金が記載されている。熱収縮の改善や内部残留応力を低減は部品の寸法精度向上に有効である。 As a copper alloy having an excellent balance between strength and conductivity, there is a Cu—Ni—Si based copper alloy (so-called Corson alloy). This alloy system can be adjusted to a high strength of 0.2% proof stress of 800 MPa or more while maintaining a relatively high conductivity (35 to 50% IACS). Patent Document 1 describes a high-strength Cu—Ni—Si based copper alloy with improved thermal shrinkage. Patent Documents 2 to 5 describe high-strength Cu—Ni—Si based copper alloys with reduced internal residual stress. Improvement of heat shrinkage and reduction of internal residual stress are effective in improving the dimensional accuracy of parts.
しかしながら発明者らの検討によれば、これらの文献に開示の銅合金は、多ピン化が進むQFNパッケージのリードフレームをはじめとする精密形状の高強度通電部品に適用するには、熱収縮の面で満足できるレベルに達していない。部品の寸法精度向上のためには素材側での更なる改善が望まれている。 However, according to the study by the inventors, the copper alloys disclosed in these documents are subject to thermal shrinkage in order to be applied to precision-shaped high-strength current-carrying parts such as lead frames of QFN packages that are becoming increasingly multi-pinned. The level is not satisfactory. In order to improve the dimensional accuracy of parts, further improvements on the material side are desired.
従来の技術では、QFNパッケージの多ピン化リードフレームのように高い寸法精度が要求される部品に加工することを考慮すると、高強度Cu−Ni−Si系銅合金板材の熱収縮を満足できるレベルまで低減することができない。本発明は、高強度および良好な導電性を有するCu−Ni−Si系銅合金において、部品加工工程の熱処理で問題となる熱収縮を従来よりも低減した銅合金板材を提供しようというものである。 In the conventional technology, considering the processing into parts that require high dimensional accuracy, such as QFN package multi-pin lead frames, a level that can satisfy the heat shrinkage of high strength Cu-Ni-Si copper alloy sheet Can not be reduced. The present invention is to provide a copper alloy sheet material in which the heat shrinkage, which is a problem in the heat treatment of the component processing process, is reduced compared to the conventional Cu-Ni-Si copper alloy having high strength and good conductivity. .
発明者らは研究の結果、高強度Cu−Ni−Si系銅合金板材の熱収縮を安定して顕著に低減するためには、(i)時効処理後に行う仕上冷間圧延のワークロールを太径のものとし、その最終パスでの圧下率を制限すること、(ii)最終的な低温焼鈍で板に付与される張力を一定範囲に厳しくコントロールするとともに、冷却速度が過大とならないように最大冷却速度を厳しく管理すること、が極めて有効であることを見出した。本発明はこのような知見に基づいて完成したものである。 As a result of research, the inventors have determined that (i) a work roll for finish cold rolling performed after aging treatment is thickened in order to stably and significantly reduce the thermal shrinkage of a high-strength Cu—Ni—Si based copper alloy sheet. Limit the rolling reduction in the final pass, and (ii) strictly control the tension applied to the plate in the final low-temperature annealing within a certain range and make sure that the cooling rate does not become excessive. It has been found that strictly controlling the cooling rate is extremely effective. The present invention has been completed based on such findings.
すなわち本発明では、質量%で、Ni:1.0〜4.5%、Si:0.1〜1.2%、Mg:0〜0.3%、Cr:0〜0.2%、Co:0〜2.0%、P:0〜0.1%、B:0〜0.05%、Mn:0〜0.2%、Sn:0〜0.5%、Ti:0〜0.5%、Zr:0〜0.2%、Al:0〜0.2%、Fe:0〜0.3%、Zn:0〜1.0%、残部Cuおよび不可避的不純物からなる組成を有する板材であって、圧延平行方向の0.2%耐力が800MPa以上、導電率が35%IACS以上であり、当該板材から圧延平行方向180mm、圧延直角方向50mmの長方形試験片を採取して500℃で10min保持する加熱試験に供したとき、下記(1)式に定義される圧延平行方向の熱収縮率λが0.020%以下となる性質を有する銅合金板材が提供される。
λ(%)=(L0−L1)/L0×100 …(1)
ここで、L0は加熱試験前の試験片の20℃における圧延平行方向長さ(mm)、L1は加熱試験後の試験片の20℃における圧延平行方向長さ(mm)である。
That is, in the present invention, in mass%, Ni: 1.0 to 4.5%, Si: 0.1 to 1.2%, Mg: 0 to 0.3%, Cr: 0 to 0.2%, Co : 0 to 2.0%, P: 0 to 0.1%, B: 0 to 0.05%, Mn: 0 to 0.2%, Sn: 0 to 0.5%, Ti: 0 to 0.0. 5%, Zr: 0 to 0.2%, Al: 0 to 0.2%, Fe: 0 to 0.3%, Zn: 0 to 1.0%, balance Cu and inevitable impurities. A rectangular test piece having a 0.2% proof stress in the rolling parallel direction of 800 MPa or more and an electrical conductivity of 35% IACS or more, and having a 180 mm parallel to the rolling direction and a 50 mm perpendicular to the rolling direction is collected from the plate. A copper alloy sheet material having a property that the thermal shrinkage ratio λ in the rolling parallel direction defined by the following formula (1) is 0.020% or less when subjected to a heating test for 10 minutes at That.
λ (%) = (L 0 −L 1 ) / L 0 × 100 (1)
Here, L 0 is the length (mm) in the rolling parallel direction at 20 ° C. of the test piece before the heating test, and L 1 is the length (mm) in the rolling parallel direction at 20 ° C. of the test piece after the heating test.
上記合金元素のうち、Mg、Cr、Co、P、B、Mn、Sn、Ti、Zr、Al、Fe、Znは任意添加元素である。上記銅合金板材は、圧延直角方向の板幅が50mm以上であるものが対象となる。このような板材製品は、そのままプレス打抜き工程に供される場合もあるし、さらにスリットされて狭幅の条材としたのち部品加工に供される場合もある。圧延平行方向の0.2%耐力は、長手方向が圧延方向に平行な引張試験片を用いてJIS Z2241:2011に従って測定したオフセット方による0.2%耐力である。 Among the above alloy elements, Mg, Cr, Co, P, B, Mn, Sn, Ti, Zr, Al, Fe, and Zn are optional additional elements. The said copper alloy board | plate material makes object the board width | variety of a rolling right-angle direction 50 mm or more. Such a plate product may be subjected to a press punching process as it is, or may be further slit to form a narrow strip and then used for part processing. The 0.2% yield strength in the rolling parallel direction is a 0.2% yield strength by an offset method measured according to JIS Z2241: 2011 using a tensile test piece whose longitudinal direction is parallel to the rolling direction.
板面(圧延面)について圧延方向に対し直角方向に測定した切断法による平均結晶粒径は例えば3〜50μmである。板厚は例えば0.03〜0.5mmの範囲とすることができるが、QFNタイプの多ピン化リードフレーム用途としては板厚0.08〜0.2mmのものが多用される傾向にある。本発明の銅合金板材はそのようなニーズに対応しうるものである。 The average crystal grain size by the cutting method measured in the direction perpendicular to the rolling direction with respect to the plate surface (rolled surface) is, for example, 3 to 50 μm. The plate thickness can be in the range of, for example, 0.03 to 0.5 mm, but as a QFN type multi-pin lead frame application, a plate thickness of 0.08 to 0.2 mm tends to be frequently used. The copper alloy sheet of the present invention can meet such needs.
また、上記銅合金板材の製造方法として、上記化学組成を有する時効処理後の中間製品板材に、ロール径(直径)70mm以上のワークロールにより、最終パスの圧下率を4〜15%として、トータル圧延率20〜80%の冷間圧延を施す工程(仕上冷間圧延工程)、
前記仕上冷間圧延工程後の板材に、5N/mm2以上30N/mm2未満の張力を付与しながら250〜550℃好ましくは330〜530℃の温度範囲で加熱した後、最大冷却速度100℃/sec以下で常温まで冷却する工程(低温焼鈍工程)、
を有する銅合金板材の製造方法が提供される。
Further, as a method for producing the copper alloy sheet, the intermediate product sheet having the above chemical composition is subjected to a work roll having a roll diameter (diameter) of 70 mm or more, and the rolling reduction of the final pass is set to 4 to 15%. A step of performing cold rolling at a rolling rate of 20 to 80% (finish cold rolling step),
The plate after the finish cold rolling step, after heating while applying 5N / mm 2 or more 30 N / mm 2 under tension 250 to 550 ° C. preferably at a temperature range of three hundred thirty to five hundred and thirty ° C., the maximum cooling rate 100 ° C. / Cooling process to room temperature at / sec or less (low temperature annealing process),
The manufacturing method of the copper alloy board | plate material which has this is provided.
なお、ある板厚t0(mm)からある板厚t1(mm)までの圧延率は、下記(2)式により求まる。
圧延率(%)=(t0−t1)/t0×100 …(2)
ある圧延パスにおける1パスでの圧延率を本明細書では特に「圧下率」と呼んでいる。
In addition, the rolling rate from a certain plate thickness t 0 (mm) to a certain plate thickness t 1 (mm) is obtained by the following equation (2).
Rolling ratio (%) = (t 0 −t 1 ) / t 0 × 100 (2)
In this specification, a rolling rate in one pass in a certain rolling pass is particularly referred to as a “rolling rate”.
また本発明では、上記の銅合金板材を材料に用いたリードフレームが提供される。 The present invention also provides a lead frame using the above copper alloy sheet as a material.
本発明に従うCu−Ni−Si系銅合金板材は、高強度および良好な導電性を具備し、かつ、部品加工段階で熱処理を施したときの「熱収縮」が極めて小さい。この板材は、QFNパッケージ用の多ピン化されたリードフレームなど、高い寸法精度が要求される通電部品に好適である。 The Cu—Ni—Si based copper alloy sheet according to the present invention has high strength and good electrical conductivity, and has very little “heat shrinkage” when heat treatment is performed in the part processing stage. This plate material is suitable for a current-carrying component that requires high dimensional accuracy, such as a multi-pin lead frame for a QFN package.
《合金組成》
本発明では、Cu−Ni−Si系銅合金を採用する。以下、合金成分に関する「%」は、特に断らない限り「質量%」を意味する。
<Alloy composition>
In the present invention, a Cu—Ni—Si based copper alloy is employed. Hereinafter, “%” regarding alloy components means “% by mass” unless otherwise specified.
Niは、Ni−Si系析出物を形成する。添加元素としてCoを含有する場合はNi−Co−Si系析出物を形成する。これらの析出物は銅合金板材の強度と導電性を向上させる。Ni−Si系析出物はNi2Siを主体とする化合物、Ni−Co−Si系析出物は(Ni,Co)2Siを主体とする化合物であると考えられる。これらの化合物を本明細書では「第二相」と言うことがある。強度向上に有効な微細な析出物粒子を十分に分散させるためには、Ni含有量を1.0%以上とする必要があり、1.3%以上とすることがより好ましい。2.0%を超える量に管理してもよい。一方、Niが過剰であると粗大な析出物が生成しやすく、熱間圧延時に割れやすい。Ni含有量は4.5%以下に制限される。4.0%未満とすることがより好ましく、3.5%以下に管理してもよい。 Ni forms Ni-Si based precipitates. When Co is contained as an additive element, a Ni—Co—Si based precipitate is formed. These precipitates improve the strength and conductivity of the copper alloy sheet. The Ni—Si based precipitate is considered to be a compound mainly composed of Ni 2 Si, and the Ni—Co—Si based precipitate is considered to be a compound mainly composed of (Ni, Co) 2 Si. These compounds are sometimes referred to herein as “second phase”. In order to sufficiently disperse fine precipitate particles effective for improving the strength, the Ni content needs to be 1.0% or more, and more preferably 1.3% or more. You may manage to the quantity exceeding 2.0%. On the other hand, if Ni is excessive, coarse precipitates are likely to be generated, and are easily cracked during hot rolling. The Ni content is limited to 4.5% or less. More preferably, the content is less than 4.0%, and may be controlled to 3.5% or less.
Siは、Ni−Si系析出物を生成する。添加元素としてCoを含有する場合はNi−Co−Si系析出物を形成する。強度向上に有効な微細な析出物粒子を十分に分散させるためには、Si含有量を0.1%以上とする必要があり、0.4%以上とすることがより好ましい。一方、Siが過剰であると粗大な析出物が生成しやすく、熱間圧延時に割れやすい。Si含有量は1.2%以下に制限される。1.0%未満に管理してもよい。 Si produces Ni—Si based precipitates. When Co is contained as an additive element, a Ni—Co—Si based precipitate is formed. In order to sufficiently disperse fine precipitate particles effective for improving the strength, the Si content needs to be 0.1% or more, and more preferably 0.4% or more. On the other hand, if Si is excessive, coarse precipitates are likely to be generated, and are easily cracked during hot rolling. The Si content is limited to 1.2% or less. You may manage to less than 1.0%.
Coは、Ni−Co−Si系の析出物を形成して、銅合金板材の強度と導電性を向上させるので、必要に応じて添加することができる。強度向上に有効な微細な析出物を十分に分散させるためには、Co含有量を0.1%以上とすることがより効果的である。ただし、Co含有量が多くなると粗大な析出物が生成しやすいので、Coを添加する場合は2.0%以下の範囲で行う。1.5%未満に管理してもよい。 Co forms Ni—Co—Si-based precipitates to improve the strength and conductivity of the copper alloy sheet, and can be added as necessary. In order to sufficiently disperse fine precipitates effective for improving the strength, it is more effective to set the Co content to 0.1% or more. However, when the Co content increases, coarse precipitates are likely to be generated. Therefore, when Co is added, it is performed within a range of 2.0% or less. You may manage to less than 1.5%.
その他の元素として、必要に応じてMg、Cr、P、B、Mn、Sn、Ti、Zr、Al、Fe、Zn等を含有させることができる。これらの元素の含有量範囲は、Mg:0〜0.3%、Cr:0〜0.2%、P:0〜0.1%、B:0〜0.05%、Mn:0〜0.2%、Sn:0〜0.5%、Ti:0〜0.5%、Zr:0〜0.2%、Al:0〜0.2%、Fe:0〜0.3%、Zn:0〜1.0%とすることが好ましい。 As other elements, Mg, Cr, P, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and the like can be contained as necessary. The content ranges of these elements are Mg: 0 to 0.3%, Cr: 0 to 0.2%, P: 0 to 0.1%, B: 0 to 0.05%, Mn: 0 to 0 0.2%, Sn: 0 to 0.5%, Ti: 0 to 0.5%, Zr: 0 to 0.2%, Al: 0 to 0.2%, Fe: 0 to 0.3%, Zn : 0 to 1.0% is preferable.
Cr、P、B、Mn、Ti、Zr、Alは合金強度を更に高め、かつ応力緩和を小さくする作用を有する。Sn、Mgは耐応力緩和性の向上に有効である。Znは銅合金板材のはんだ付け性および鋳造性を改善する。Fe、Cr、Zr、Ti、Mnは不可避的不純物として存在するS、Pbなどと高融点化合物を形成しやすく、また、B、P、Zr、Tiは鋳造組織の微細化効果を有し、熱間加工性の改善に寄与しうる。 Cr, P, B, Mn, Ti, Zr, and Al have a function of further increasing the alloy strength and reducing stress relaxation. Sn and Mg are effective in improving the stress relaxation resistance. Zn improves the solderability and castability of the copper alloy sheet. Fe, Cr, Zr, Ti, and Mn are easy to form a high melting point compound with S, Pb, etc. present as inevitable impurities, and B, P, Zr, and Ti have a refinement effect on the cast structure, It can contribute to the improvement of inter-workability.
Mg、Cr、P、B、Mn、Sn、Ti、Zr、Al、Fe、Znの1種または2種以上を含有させる場合は、それらの合計含有量を0.01%以上とすることがより効果的である。ただし、多量に含有させると、熱間または冷間加工性に悪影響を与え、かつコスト的にも不利となる。これら任意添加元素の総量は1.2%以下とすることが望ましく、1.0%以下とすることがより望ましい。 When including one or more of Mg, Cr, P, B, Mn, Sn, Ti, Zr, Al, Fe, and Zn, the total content thereof should be 0.01% or more. It is effective. However, if it is contained in a large amount, it adversely affects hot or cold workability and is disadvantageous in terms of cost. The total amount of these optional added elements is preferably 1.2% or less, and more preferably 1.0% or less.
《特性》
〔熱収縮〕
高強度化されたCu−Ni−Si系銅合金板材の金属マトリックスには多くの転位が導入されている。転位のような格子欠陥が導入されると結晶格子の体積が若干膨張する。加工素材である板材製品を成形加工したリードフレーム部材は、その成形加工後に歪取り焼鈍が施されたり、パッケージング化の際に加熱を受けたりして、半導体部品が完成するまでの段階で可動転位が動きうる温度域に加熱される場合が多い。加熱により可動転位が動いて金属マトリックスの内部歪が開放されると、格子欠陥の密度が低減することにより結晶格子の体積が収縮する。この種の収縮現象を本明細書では「熱収縮」と呼んでいる。熱収縮は部品の寸法精度を低下させる要因となる。従って、QFNタイプの多ピン化リードフレームをはじめ、特に高い寸法精度が要求される用途では、従来にも増して熱収縮の小さい板状素材が要求される。
"Characteristic"
[Heat shrinkage]
Many dislocations are introduced into the metal matrix of the Cu-Ni-Si-based copper alloy sheet that has been strengthened. When lattice defects such as dislocations are introduced, the volume of the crystal lattice expands slightly. Lead frame members formed by processing plate materials, which are processed materials, can be moved until the semiconductor parts are completed by undergoing strain relief annealing after the forming process or by being heated during packaging. It is often heated to a temperature range where dislocations can move. When the movable dislocations move by heating and the internal strain of the metal matrix is released, the density of lattice defects is reduced and the volume of the crystal lattice contracts. This type of shrinkage phenomenon is referred to herein as “thermal shrinkage”. Thermal shrinkage is a factor that reduces the dimensional accuracy of the part. Therefore, in applications that require particularly high dimensional accuracy, such as QFN type multi-pin lead frames, a plate-like material with smaller thermal shrinkage than conventional ones is required.
本発明に従う高強度Cu−Ni−Si系銅合金板材はそのような要求に応えるべく、熱収縮の低減を図ったものである。具体的には、当該板材から圧延平行方向180mm、圧延直角方向50mmの長方形試験片を採取して500℃で10min保持する加熱試験に供したとき、下記(1)式に定義される圧延平行方向の熱収縮率λが0.020%以下となる性質を有している。
λ(%)=(L0−L1)/L0×100 …(1)
ここで、L0は加熱試験前の試験片の20℃における圧延平行方向長さ(mm)、L1は加熱試験後の試験片の20℃における圧延平行方向長さ(mm)である。
The high-strength Cu—Ni—Si copper alloy sheet according to the present invention is intended to reduce thermal shrinkage in order to meet such demands. Specifically, when a rectangular test piece having a rolling parallel direction of 180 mm and a rolling perpendicular direction of 50 mm is collected from the plate material and subjected to a heating test held at 500 ° C. for 10 minutes, the rolling parallel direction defined by the following formula (1) Has a property that the thermal shrinkage ratio λ is 0.020% or less.
λ (%) = (L 0 −L 1 ) / L 0 × 100 (1)
Here, L 0 is the length (mm) in the rolling parallel direction at 20 ° C. of the test piece before the heating test, and L 1 is the length (mm) in the rolling parallel direction at 20 ° C. of the test piece after the heating test.
圧延平行方向の0.2%耐力800MPa以上に調整された高強度Cu−Ni−Si系銅合金板材(板厚が例えば0.03〜0.5mm)において、上記の熱収縮率λが0.020%以下に抑えられているものは、同等強度レベルの従来材と比較して顕著な熱収縮低減性能を有している。この熱収縮率λが0.010%以下であることが一層効果的である。熱収縮の顕著な低減は、後述のように、仕上冷間圧延の条件および低温焼鈍の条件を厳しく管理することにより実現できる。 In a high-strength Cu—Ni—Si-based copper alloy sheet (sheet thickness is, for example, 0.03 to 0.5 mm) adjusted to a 0.2% proof stress of 800 MPa or more in the rolling parallel direction, the thermal shrinkage ratio λ is 0.0. What is suppressed to 020% or less has remarkable thermal shrinkage reduction performance as compared with a conventional material having an equivalent strength level. It is more effective that the thermal shrinkage ratio λ is 0.010% or less. As will be described later, the remarkable reduction in heat shrinkage can be realized by strictly managing the conditions of finish cold rolling and the conditions of low temperature annealing.
なお、発明者らの検討によれば、単に金属マトリックスの内部残留応力を低減するだけでは、熱収縮を安定して顕著に低減することは困難である。「残留応力の低減」と「熱収縮の低減」がストレートに対応しない理由については必ずしも明確ではないが、熱収縮が実際に小さい材料は、残留応力を増大させている種々の要因の中でも特に「可動転位の残存量」が少なくなっているものと推察される。 According to the study by the inventors, it is difficult to stably and significantly reduce the thermal shrinkage simply by reducing the internal residual stress of the metal matrix. The reason why “reduced residual stress” and “reduced thermal shrinkage” do not correspond straight is not necessarily clear, but materials with actually small thermal shrinkage are particularly “among other factors that increase residual stress. It is inferred that the “residual amount of movable dislocations” is decreasing.
〔平均結晶粒径〕
平均結晶粒径は基本的に小さいほど強度の向上に有利であるが、平均結晶粒径が小さすぎると析出物が分散せず強度が低下しやすい。種々検討の結果、最終的な板材製品において、板面(圧延面)について圧延方向に対し直角方向に測定した切断法による平均結晶粒径が3〜50μmであることがより望ましく、5〜30μmであることが一層好ましい。
[Average crystal grain size]
The smaller the average crystal grain size is, the more advantageous it is for improving the strength. However, if the average crystal grain size is too small, precipitates are not dispersed and the strength tends to decrease. As a result of various studies, in the final plate product, it is more desirable that the average crystal grain size by the cutting method measured in the direction perpendicular to the rolling direction on the plate surface (rolled surface) is 3 to 50 μm, and 5 to 30 μm. More preferably it is.
〔強度・導電性〕
Cu−Ni−Si系銅合金板材をリードフレーム等の通電部品の素材に用いるためには、圧延平行方向(LD)の0.2%耐力800MPa以上の強度レベルが望まれる。一方、通電部品の薄肉化のためには、導電性が良好であるも重要な要件となる。具体的には、導電率35%IACS以上であることが望ましく、40%IACS以上であることがより好ましい。
[Strength / Conductivity]
In order to use a Cu—Ni—Si based copper alloy sheet as a material for a current-carrying part such as a lead frame, a strength level of 0.2 MPa in the rolling parallel direction (LD) of 800 MPa or more is desired. On the other hand, in order to reduce the thickness of the current-carrying parts, it is an important requirement even though the conductivity is good. Specifically, the electrical conductivity is desirably 35% IACS or more, and more preferably 40% IACS or more.
《製造方法》
以上説明した銅合金板材は、例えば以下のような製造工程により作ることができる。
「溶解・鋳造→熱間圧延→冷間圧延→溶体化処理→時効処理→仕上冷間圧延→(形状矯正)→低温焼鈍」
これに限らず、必要に応じて工程中に熱処理および冷間圧延を加えることができる。
本発明では熱収縮の小さい板材製品を得るために、特に「仕上冷間圧延」、「低温焼鈍」の最終2工程における作り込みが重要である。時効処理までの工程には特にこだわる必要はなく、一般的なCu−Ni−Si系銅合金の製造条件を採用すればよい。
なお、上記工程中には記載していないが、熱間圧延後には必要に応じて面削が行われ、各熱処理後には必要に応じて酸洗、研磨、あるいは更に脱脂が行われる。また、仕上冷間圧延後には必要に応じてテンションレベラーによる形状矯正が行われる。以下、各工程について説明する。
"Production method"
The copper alloy sheet material described above can be produced by the following manufacturing process, for example.
“Melting / Casting → Hot Rolling → Cold Rolling → Solution Treatment → Aging Treatment → Finish Cold Rolling → (Shape Correction) → Low Temperature Annealing”
Not only this but heat processing and cold rolling can be added in the process as needed.
In the present invention, in order to obtain a plate product having a small thermal shrinkage, it is particularly important to make it in the final two steps of “finish cold rolling” and “low temperature annealing”. There is no need to pay particular attention to the steps up to the aging treatment, and general production conditions for a Cu—Ni—Si based copper alloy may be adopted.
Although not described in the above steps, chamfering is performed as necessary after hot rolling, and pickling, polishing, or further degreasing is performed as necessary after each heat treatment. Further, after finish cold rolling, shape correction by a tension leveler is performed as necessary. Hereinafter, each step will be described.
〔溶解・鋳造〕
連続鋳造、半連続鋳造等により鋳片を製造すればよい。Siなどの酸化を防止するために、不活性ガス雰囲気または真空溶解炉で行うのがよい。
[Melting / Casting]
The slab may be manufactured by continuous casting, semi-continuous casting, or the like. In order to prevent oxidation of Si or the like, it is preferable to carry out in an inert gas atmosphere or a vacuum melting furnace.
〔熱間圧延〕
熱間圧延は通常の手法に従えばよい。熱間圧延前の鋳片加熱は例えば900〜1020℃で1〜5hとすることができる。トータルの熱間圧延率は例えば70〜97%とすればよい。最終パスの圧延温度は700℃以上とすることが好ましい。熱間圧延終了後には、水冷などにより急冷することが好ましい。
(Hot rolling)
Hot rolling may follow a normal method. The slab heating before hot rolling can be 1 to 5 hours at 900 to 1020 ° C., for example. The total hot rolling rate may be, for example, 70 to 97%. The rolling temperature in the final pass is preferably 700 ° C. or higher. After the hot rolling is finished, it is preferable to quench by water cooling or the like.
〔冷間圧延〕
溶体化処理前の冷間圧延により、板厚の減少および歪エネルギー(転位)の導入を図る。その歪エネルギーは、溶体化処理での第二相の溶体化に有効に作用する。必要に応じて、中間焼鈍を挟んだ複数回の冷間圧延を行うことができる。溶体化処理前の冷間圧延率(中間焼鈍を挟んで冷間圧延を行う場合は最後の中間焼鈍後の冷間圧延率)は、例えば70%以上とすることが効果的である。ミルパワー等による設備的な許容範囲において、通常99%以下の圧延率範囲で行えばよい。
(Cold rolling)
By cold rolling before the solution treatment, reduction of the plate thickness and introduction of strain energy (dislocation) are attempted. The strain energy effectively acts on the solution of the second phase in the solution treatment. If necessary, cold rolling can be performed a plurality of times with intermediate annealing. It is effective to set the cold rolling rate before the solution treatment (the cold rolling rate after the final intermediate annealing when performing cold rolling with the intermediate annealing interposed therebetween) to, for example, 70% or more. The rolling tolerance range of 99% or less is usually used in the facility tolerance range such as mill power.
〔溶体化処理〕
溶体化処理を行い、第二相を十分に固溶させる。溶体化処理条件は、加熱保持温度を850〜1020℃の範囲に設定すればよい。850〜980℃の範囲がより好ましい。上記温度範囲に保持する時間は10sec〜10minの範囲で設定すればよい。溶体化処理後の板材において、上述の方法により求まる平均結晶粒径が3〜25μm、より好ましくは5〜20μm、更に好ましくは5〜17μmとなるように、加熱温度および加熱時間を調整することが望ましい。再固溶、再結晶化を確実に行い、かつ平均結晶粒径を上記範囲に調整するための最適な溶体化条件は組成や溶体化処理前の製造条件によって変動するが、予め予備実験により組成や冷間圧延率に応じた最適な溶体化処理ヒートパターン条件を把握しておくことにより、適正条件範囲に設定することが容易となる。なお、530℃から300℃までの平均冷却速度は100℃/sec以上とすることが望ましい。
[Solution treatment]
A solution treatment is performed to sufficiently dissolve the second phase. What is necessary is just to set the heat treatment temperature in the range of 850-1020 degreeC as solution treatment conditions. The range of 850-980 degreeC is more preferable. What is necessary is just to set the time hold | maintained in the said temperature range in the range of 10 sec-10min. In the plate material after solution treatment, the heating temperature and the heating time can be adjusted so that the average crystal grain size determined by the above-mentioned method is 3 to 25 μm, more preferably 5 to 20 μm, and still more preferably 5 to 17 μm. desirable. The optimal solution conditions for ensuring re-solution and recrystallization and adjusting the average crystal grain size to the above range will vary depending on the composition and manufacturing conditions before solution treatment, In addition, by grasping the optimum solution treatment heat pattern condition according to the cold rolling rate, it becomes easy to set the appropriate condition range. The average cooling rate from 530 ° C. to 300 ° C. is preferably 100 ° C./sec or more.
〔時効処理〕
次いで時効処理を行い、強度に寄与する微細な析出物粒子を析出させる。合金組成に応じて時効で硬さがピークになる温度、時間を予め調整して条件を決めるのが好ましい。具体的には、時効温度は400〜550℃とすることが好ましく、425〜525℃とすることがより好ましい。時効処理時間は、3〜12hの範囲で良好な結果が得られる。時効処理中の表面酸化を極力抑制する場合には、水素、窒素またはアルゴン雰囲気を使うことができる。
[Aging treatment]
Next, an aging treatment is performed to precipitate fine precipitate particles that contribute to the strength. The conditions are preferably determined by adjusting in advance the temperature and time at which the hardness reaches its peak due to aging according to the alloy composition. Specifically, the aging temperature is preferably 400 to 550 ° C, and more preferably 425 to 525 ° C. Good results are obtained when the aging treatment time is in the range of 3 to 12 hours. In order to suppress the surface oxidation during the aging treatment as much as possible, a hydrogen, nitrogen or argon atmosphere can be used.
〔仕上冷間圧延〕
仕上冷間圧延は強度レベル(特に0.2%耐力)の向上に有効である。仕上冷間圧延率(トータル圧延率)は20%以上とすることが効果的であり25%以上とすることがより効果的である。仕上冷間圧延率が高くなると低温焼鈍時に強度が低下しやすいので80%以下の圧延率とすることが好ましく、70%以下とすることがより好ましい。65%以下の範囲に管理してもよい。最終的な板厚としては、例えば0.03〜0.50mm程度の範囲で設定することができ、0.08〜0.20mmに管理してもよい。
[Finish cold rolling]
Finish cold rolling is effective in improving the strength level (particularly 0.2% yield strength). The finish cold rolling rate (total rolling rate) is effectively 20% or more, and more preferably 25% or more. When the finish cold rolling rate increases, the strength tends to decrease during low-temperature annealing, so the rolling rate is preferably 80% or less, and more preferably 70% or less. You may manage in the range of 65% or less. The final plate thickness can be set, for example, in the range of about 0.03 to 0.50 mm, and may be controlled to 0.08 to 0.20 mm.
通常、冷間圧延での圧下率を増大させるためには径の小さいワークロールを使用することが有利である。しかし、発明者らの検討によれば、熱収縮の小さい板材製品を製造するためには仕上冷間圧延で径の大きいワークロールを使用することが極めて有効であることがわかった。大径ワークロールを使用することによって、同じ圧延率を従来の小径ワークロールで行った場合に比べ、可動転位の導入量が少なくなるのではないかと推察される。種々検討の結果、直径70mm以上の大径ワークロールを使用することによって熱収縮率λが0.020%以下の板材を得ることが可能となる。特に直径80mm以上のワークロールを用いた場合において、後述の低温焼鈍条件の制限を厳しく管理すれば、熱収縮率λが0.010%以下の板材を作り分けることができる。一方、ワークロール径が過大であると板厚が薄くなるに従って圧下率を十分に確保するために必要なミルパワーが増大し、所定の板厚に仕上げるうえで不利となる。冷間圧延機のミルパワーおよび目標板厚に応じて使用する大径ワークロール設定上限を定めることができる。例えば、トータル圧延率を20%以上として上記板厚範囲の板材を得る場合、直径100mm以下のワークロールを使用することが好ましい。 Usually, it is advantageous to use a work roll having a small diameter in order to increase the rolling reduction in cold rolling. However, according to the study by the inventors, it has been found that it is extremely effective to use a work roll having a large diameter in finish cold rolling in order to produce a plate product having a small thermal shrinkage. By using a large-diameter work roll, it is presumed that the introduction amount of movable dislocations may be reduced as compared with the case where the same rolling rate is performed with a conventional small-diameter work roll. As a result of various studies, it is possible to obtain a plate material having a thermal shrinkage ratio λ of 0.020% or less by using a large-diameter work roll having a diameter of 70 mm or more. In particular, when a work roll having a diameter of 80 mm or more is used, a plate material having a thermal shrinkage ratio λ of 0.010% or less can be created by strictly managing the restriction of low-temperature annealing conditions described later. On the other hand, if the work roll diameter is excessively large, the mill power necessary to sufficiently secure the rolling reduction increases as the plate thickness decreases, which is disadvantageous in finishing to a predetermined plate thickness. The upper limit of the large-diameter work roll to be used can be determined according to the mill power and the target plate thickness of the cold rolling mill. For example, when obtaining a plate material in the above plate thickness range with a total rolling rate of 20% or more, it is preferable to use a work roll having a diameter of 100 mm or less.
また、熱収縮を低減させるためには、仕上冷間圧延の最終パスにおける圧下率を15%以下とすることが極めて有効である。12%以下、あるいは10%未満とすることがより好ましい。ただし、最終パスでの圧下率が低すぎると生産性の低下に繋がるので、4%以上の圧下率を確保する。 In order to reduce thermal shrinkage, it is extremely effective to set the rolling reduction in the final pass of finish cold rolling to 15% or less. More preferably, it is 12% or less or less than 10%. However, if the rolling reduction rate in the final pass is too low, productivity will be reduced, so a rolling reduction rate of 4% or more is secured.
〔形状矯正〕
仕上冷間圧延を終えた板材に対して、最終的な低温焼鈍を施す前に、テンションレベラーによる形状矯正を施しても構わない。テンションレベラーは圧延方向に張力を付与しながら板材を複数の形状矯正ロールによって曲げ伸ばす装置である。テンションレベラーを通板する場合には伸び率が1.5%以下となる条件とすることが望ましい。
[Shape correction]
The plate material that has undergone finish cold rolling may be subjected to shape correction by a tension leveler before final low temperature annealing. A tension leveler is a device that bends and stretches a plate material with a plurality of shape correction rolls while applying tension in the rolling direction. In the case of passing a tension leveler, it is desirable that the elongation is 1.5% or less.
〔低温焼鈍〕
仕上冷間圧延後には、通常、板条材の残留応力の低減や曲げ加工性の向上、空孔やすべり面上の転位の低減による耐応力緩和性向上を目的として低温焼鈍が施される。ただし、本発明では熱収縮の小さい板材製品を得るために、最終的な熱処理である低温焼鈍の条件を厳しく制限する必要がある。
[Low temperature annealing]
After finish cold rolling, low temperature annealing is usually performed for the purpose of reducing the residual stress of the strip material, improving the bending workability, and improving the stress relaxation resistance by reducing the dislocations on the pores and the sliding surface. However, in the present invention, in order to obtain a plate product having a small heat shrinkage, it is necessary to strictly limit the conditions for low-temperature annealing, which is the final heat treatment.
第1に、低温焼鈍の加熱温度を250〜550℃とする。250℃より低温では可動転位の残存量を十分に低減すること難しく、熱収縮の低減効果が不十分となる。550℃より高温になると材料が軟化し所定の高強度を十分に確保することが難しくなる。330〜530℃の範囲とすることがより好ましい。上記温度での保持時間は5〜600secの範囲で設定すればよい。 1stly, the heating temperature of low-temperature annealing shall be 250-550 degreeC. At a temperature lower than 250 ° C., it is difficult to sufficiently reduce the remaining amount of movable dislocations, and the effect of reducing thermal shrinkage becomes insufficient. When the temperature is higher than 550 ° C., the material becomes soft and it is difficult to sufficiently secure a predetermined high strength. It is more preferable to set it as the range of 330-530 degreeC. The holding time at the above temperature may be set in the range of 5 to 600 seconds.
第2に、上記温度での加熱中に板材に付与される張力を5N/mm2以上30N/mm2未満の範囲にコントロールする。連続ラインにおいては、張力の方向は圧延平行方向となる。張力が5N/mm2を下回ると特に高強度材では可動転位の低減効果が不足し、熱収縮の顕著な低減を安定して実現することが難しくなる。30N/mm2以上になると特に高強度材では残留応力が大きくなりやすく、熱収縮の低減にはマイナス要因となる。25N/mm2以下とすることがより好ましい。なお、上述の仕上冷間圧延にて直径80mm以上のワークロールを用い、かつ当該低温焼鈍での張力を5N/mm2以上25N/mm2以下の範囲に厳しくコントロールすることによって、熱収縮率λが0.010%という、極めて熱収縮の小さい板材製品を作り分けることができる。 Second, to control the tension applied to the sheet material during heating in the temperature range below 5N / mm 2 or more 30 N / mm 2. In a continuous line, the direction of tension is the rolling parallel direction. When the tension is less than 5 N / mm 2 , particularly in a high-strength material, the effect of reducing movable dislocation is insufficient, and it becomes difficult to stably realize a remarkable reduction in heat shrinkage. If it is 30 N / mm 2 or more, the residual stress tends to increase particularly in the case of a high-strength material, which becomes a negative factor in reducing thermal shrinkage. More preferably, it is 25 N / mm 2 or less. Incidentally, by strict control tension 5N / mm 2 or more 25 N / mm 2 or less in the range in the use of the above work roll diameter 80mm at the aforementioned finish cold rolling, and the low-temperature annealing, thermal shrinkage λ Of 0.010%, which can make a plate material product with extremely small heat shrinkage.
第3に、最大冷却速度100℃/sec以下で常温まで冷却する。すなわち、上記加熱後に100℃/secを超える冷却速度とならないように常温(5〜35℃)まで降温させる。最大冷却速度が100℃/secを超えると、急激な冷却により可動転位が多く残存し、熱収縮の低減が不十分となる。冷却時の通板方向に対して板面直角方向(圧延直角方向)の温度分布が不均一になり、十分な平坦性が得られない。加熱後の冷却は例えば冷却ガスを用いた強制冷却とすることができる。その場合、冷却ファン回転数、冷却ゾーンの雰囲気温度、冷却ガスの種類をコントロールすることにより最大冷却速度を100℃/sec以下の範囲に収めることができる。冷却ガスとしては水素、窒素、空気などが使用できる。 Third, it is cooled to room temperature at a maximum cooling rate of 100 ° C./sec or less. That is, the temperature is lowered to room temperature (5 to 35 ° C.) so that the cooling rate does not exceed 100 ° C./sec after the heating. When the maximum cooling rate exceeds 100 ° C./sec, a large number of movable dislocations remain due to rapid cooling, resulting in insufficient reduction of heat shrinkage. The temperature distribution in the direction perpendicular to the plate surface (in the direction perpendicular to rolling) with respect to the sheet passing direction during cooling becomes non-uniform, and sufficient flatness cannot be obtained. Cooling after heating can be forced cooling using a cooling gas, for example. In that case, the maximum cooling rate can be kept within a range of 100 ° C./sec or less by controlling the number of rotations of the cooling fan, the ambient temperature of the cooling zone, and the type of the cooling gas. As the cooling gas, hydrogen, nitrogen, air, or the like can be used.
表1に示す組成の銅合金を溶製し、縦型半連続鋳造機を用いて鋳造した。得られた鋳片を1000℃で3h加熱したのち抽出して、厚さ10mmまで熱間圧延した後、水冷した。トータルの熱間圧延率は90〜95%、熱間圧延終了温度は700〜750℃である。熱間圧延後、表層の酸化層を機械研磨により除去(面削)した。次いで、圧延率90〜99%で冷間圧延を行った。その後、表2に示す条件で溶体化処理、時効処理、仕上冷間圧延、および低温焼鈍を行い、板厚0.15mm、圧延直角方向の板幅W0が510mmの板材製品(供試材)を得た。 A copper alloy having the composition shown in Table 1 was melted and cast using a vertical semi-continuous casting machine. The obtained slab was heated at 1000 ° C. for 3 hours, extracted, hot-rolled to a thickness of 10 mm, and then water-cooled. The total hot rolling rate is 90 to 95%, and the hot rolling finish temperature is 700 to 750 ° C. After hot rolling, the surface oxide layer was removed (faced) by mechanical polishing. Subsequently, cold rolling was performed at a rolling rate of 90 to 99%. Thereafter, solution treatment, aging treatment, finish cold rolling, and low-temperature annealing were performed under the conditions shown in Table 2, and a plate product having a plate thickness of 0.15 mm and a plate width W 0 in the direction perpendicular to the roll of 510 mm (test material) Got.
なお、低温焼鈍はカテナリー炉を連続通板したのち、空冷する方法で行った。加熱時間は10〜90secである。加熱中の張力は炉内を通板中の材料のカテナリー曲線(炉内通板方向両端部および中央部の板の高さ位置、並びに炉内長)から算出した。冷却中の板表面の温度を通板方向の種々の位置で測定することにより、横軸に時間、縦軸に温度をとった冷却温度曲線を求めた。1つの供試材においては通板中の板の全長にわたって同じ条件で冷却しているので、この冷却曲線の最大勾配を当該供試材の最大冷却速度として採用した。供試材毎の冷却速度は、冷却雰囲気、ファン回転数をコントロールすること、また冷却温度を多段階で下げることによって変化させた。 The low-temperature annealing was performed by air cooling after continuously passing through a catenary furnace. The heating time is 10 to 90 sec. The tension during heating was calculated from the catenary curve of the material in the plate passing through the furnace (the height position of the plate at both ends and the center of the plate passing through the furnace and the length in the furnace). By measuring the temperature of the plate surface during cooling at various positions in the plate direction, a cooling temperature curve was obtained with time on the horizontal axis and temperature on the vertical axis. Since one test material was cooled under the same conditions over the entire length of the plate in the plate, the maximum gradient of this cooling curve was adopted as the maximum cooling rate of the test material. The cooling rate for each specimen was changed by controlling the cooling atmosphere and fan rotation speed, and by lowering the cooling temperature in multiple stages.
〔導電率〕
JIS H0505に従って各供試材の導電率を測定した。
〔圧延方向の0.2%耐力〕
各供試材から圧延方向(LD)の引張試験片(JIS 5号)を採取し、試験数n=3でJIS Z2241に準拠した引張試験行い、0.2%耐力を測定した。n=3の平均値を当該供試材の成績値とした。
〔conductivity〕
The electrical conductivity of each test material was measured according to JIS H0505.
[0.2% proof stress in the rolling direction]
A tensile test piece (JIS No. 5) in the rolling direction (LD) was taken from each test material, and a tensile test based on JIS Z2241 was performed with the number of tests n = 3, and a 0.2% yield strength was measured. The average value of n = 3 was defined as the result value of the test material.
〔熱収縮〕
各供試材から圧延平行方向長さ180mm、圧延直角方向長さ50mmの長方形試験片を切り出し、窒素雰囲気500℃で10min保持する加熱試験に供した。常温から500℃までの昇温時間は約30secである。加熱後の冷却は、試験片を常温の炉外に出して、水平な台の上に静置して放冷した。加熱試験前の試験片の20℃における圧延平行方向長さL0、および加熱試験後の試験片の20℃における圧延平行方向長さL1から、前記(1)式により熱収縮率λを求めた。L0およびL1は、試験片を水平盤上に置き、試験片の幅中央位置(すなわち圧延直角方向の中央位置)における試験片の圧延平行方向長さをレーザー変位計により測定する方法で求めた。試験数n=3の測定値のうち、最も大きいλ値を当該供試材の成績値として採用した。
[Heat shrinkage]
A rectangular test piece having a length of 180 mm in the rolling parallel direction and a length of 50 mm in the direction perpendicular to the rolling was cut out from each sample material and subjected to a heating test that was held at 500 ° C. for 10 minutes in a nitrogen atmosphere. The heating time from room temperature to 500 ° C. is about 30 seconds. For cooling after heating, the test piece was taken out of the furnace at room temperature and left on a horizontal table to cool. The heat shrinkage ratio λ is obtained by the above equation (1) from the length L 0 in the rolling parallel direction at 20 ° C. of the test piece before the heating test and the length L 1 in the rolling parallel direction at 20 ° C. of the test piece after the heating test. It was. L 0 and L 1 are obtained by a method in which the test piece is placed on a horizontal plate and the length in the rolling parallel direction of the test piece at the center position in the width direction of the test piece (that is, the central position in the direction perpendicular to the rolling direction) is measured with a laser displacement meter. It was. Among the measured values of the number of tests n = 3, the largest λ value was adopted as the result value of the test material.
〔残留応力〕
各供試材から幅10mm×長さ200mmの試験片(ただし、長手方向が圧延方向に一致)を切り出し、Treuting−Read法(参考文献:米谷茂、「残留応力の発生と対策」、株式会社養賢堂、p.54−56、1975年)により残留応力を求めた。具体的には、特許文献2の段落0029、0030に開示される方法に従った。試験数n=3の平均値を当該供試材の成績値とした。
[Residual stress]
A test piece having a width of 10 mm and a length of 200 mm was cut out from each specimen (however, the longitudinal direction coincides with the rolling direction), and the Truting-Read method (reference: Shigeru Yoneya, “Generation and countermeasures of residual stress”, Co., Ltd. Residual stress was determined by Yokendo, p.54-56, 1975). Specifically, the method disclosed in paragraphs 0029 and 0030 of Patent Document 2 was followed. The average value of the number of tests n = 3 was defined as the result value of the test material.
〔平均結晶粒径〕
各供試材の板面(圧延面)を研磨しエッチングした表面の光学顕微鏡観察によりJIS H0501の切断法で圧延面に対し平行方向、かつ圧延方向に対し直角方向の既知長さの線分によって完全に切られる結晶粒数を数えることにより平均結晶粒径を求めた。ただし、測定対象の結晶粒の総数を100個以上とする。双晶境界は結晶粒界とみなさない。平均結晶粒径を測定するための光学顕微鏡観察においては、観察領域を300μm×300μmの矩形領域とした。
これらの結果を表2に示す。
[Average crystal grain size]
By observing the surface of the specimen (rolled surface) polished and etched with an optical microscope, a line segment of a known length in a direction parallel to the rolled surface and perpendicular to the rolled direction by the cutting method of JIS H0501. The average crystal grain size was determined by counting the number of crystal grains that were completely cut. However, the total number of crystal grains to be measured is 100 or more. Twin boundaries are not considered grain boundaries. In the optical microscope observation for measuring the average crystal grain size, the observation area was a rectangular area of 300 μm × 300 μm.
These results are shown in Table 2.
表2からわかるように、本発明例の銅合金板材はいずれもLDの0.2%耐力が800MPa以上の高強度を有するとともに、熱収縮率が0.020%以下に低減されている。残留応力は100MPa以下であり、LDの0.2%耐力800MPa以上の強度レベルを有するCu−Ni−Si系銅合金板材としては低い値である。導電性も良好である。これらの板材は、QFNタイプの多ピン化リードフレームをはじめとする高い寸法精度が要求される精密通電部品の素材として極めて有用である。なお、仕上冷間圧延でのワークロール径を80mm以上とし、かつ低温焼鈍での張力を25N/mm2以下とすることにより、熱収縮率0.010%以下を安定して実現できることがわかる。 As can be seen from Table 2, each of the copper alloy sheet materials of the present invention has a high strength with a 0.2% proof stress of LD of 800 MPa or more and a thermal shrinkage rate reduced to 0.020% or less. The residual stress is 100 MPa or less, which is a low value as a Cu—Ni—Si based copper alloy sheet having a strength level of 0.2% proof stress of 800 MPa or more. The conductivity is also good. These plate materials are extremely useful as materials for precision energized parts such as QFN type multi-pin lead frames that require high dimensional accuracy. In addition, it turns out that heat shrinkage rate 0.010% or less can be stably implement | achieved by making the work roll diameter in finish cold rolling into 80 mm or more and the tension | tensile_strength in low temperature annealing to 25 N / mm < 2 > or less.
これに対し、比較例No.31は仕上冷間圧延でのトータル圧延率が低すぎたので強度レベルが低かった。No.32は低温焼鈍の加熱温度が高すぎたので強度が低下した。No.33、34は仕上冷間圧延の最終パスでの圧下率が過大であったので板材の熱収縮が大きかった。No.35、36は仕上冷間圧延に使用したワークロールの径が過小であったので熱収縮が大きかった。No.37はNi含有量が過大であり、またNo.39はSi含有量が過大であるため、これらは導電性に劣った。No.38はNi含有量が過小であり、またNo.40はSi含有量が過小であるため、これらは強度が低かった。No.41は低温焼鈍での加熱時の張力が過大であるため熱収縮が大きかった。No.42、43は低温焼鈍での最大冷却速度が過大であったので板材の熱収縮が大きかった。No.44は低温焼鈍の加熱温度が低すぎたので熱収縮が大きかった。No.45は仕上冷間圧延率が高すぎたので低温焼鈍時に強度が低下した。No.46は低温焼鈍時の張力が低すぎたので熱収縮が大きかった。 On the other hand, Comparative Example No. 31 had a low strength level because the total rolling ratio in the finish cold rolling was too low. In No. 32, the strength decreased because the heating temperature for low-temperature annealing was too high. In Nos. 33 and 34, the reduction ratio in the final pass of the finish cold rolling was excessive, so the thermal contraction of the plate material was large. In Nos. 35 and 36, the diameter of the work roll used for the finish cold rolling was too small, so the heat shrinkage was large. Since No. 37 has an excessive Ni content, and No. 39 has an excessive Si content, these were inferior in conductivity. No. 38 had a low Ni content, and No. 40 had a low Si content, so these were low in strength. No. 41 had a large thermal shrinkage due to excessive tension during heating in low-temperature annealing. In Nos. 42 and 43, since the maximum cooling rate in the low-temperature annealing was excessive, the thermal contraction of the plate material was large. No. 44 had a large thermal shrinkage because the heating temperature of the low-temperature annealing was too low. In No. 45, since the finish cold rolling rate was too high, the strength decreased during low temperature annealing. No. 46 had a large thermal shrinkage because the tension during low-temperature annealing was too low.
Claims (5)
λ(%)=(L0−L1)/L0×100 …(1)
ここで、L0は加熱試験前の試験片の20℃における圧延平行方向長さ(mm)、L1は加熱試験後の試験片の20℃における圧延平行方向長さ(mm)である。 In mass%, Ni: 1.0 to 4.5%, Si: 0.1 to 1.2%, Mg: 0 to 0.3%, Cr: 0 to 0.2%, Co: 0 to 2. 0%, P: 0 to 0.1%, B: 0 to 0.05%, Mn: 0 to 0.2%, Sn: 0 to 0.5%, Ti: 0 to 0.5%, Zr: A plate material having a composition comprising 0 to 0.2%, Al: 0 to 0.2%, Fe: 0 to 0.3%, Zn: 0 to 1.0%, the balance Cu and unavoidable impurities, Heating of 0.2% proof stress in the rolling parallel direction of 800 MPa or more, electrical conductivity of 35% IACS or more, taking a rectangular test piece of 180 mm in the rolling parallel direction and 50 mm in the rolling perpendicular direction from the plate material, and holding at 500 ° C. for 10 minutes A copper alloy sheet having a property that when subjected to the test, the heat shrinkage ratio λ in the rolling parallel direction defined by the following formula (1) is 0.020% or less.
λ (%) = (L 0 −L 1 ) / L 0 × 100 (1)
Here, L 0 is the length (mm) in the rolling parallel direction at 20 ° C. of the test piece before the heating test, and L 1 is the length (mm) in the rolling parallel direction at 20 ° C. of the test piece after the heating test.
前記仕上冷間圧延工程後の板材に、5N/mm2以上30N/mm2未満の張力を付与しながら250〜550℃の温度範囲で加熱した後、最大冷却速度100℃/sec以下で常温まで冷却する工程(低温焼鈍工程)、
を有する銅合金板材の製造方法。 In mass%, Ni: 1.0 to 4.5%, Si: 0.1 to 1.2%, Mg: 0 to 0.3%, Cr: 0 to 0.2%, Co: 0 to 2. 0%, P: 0 to 0.1%, B: 0 to 0.05%, Mn: 0 to 0.2%, Sn: 0 to 0.5%, Ti: 0 to 0.5%, Zr: Intermediate after aging treatment having a composition consisting of 0 to 0.2%, Al: 0 to 0.2%, Fe: 0 to 0.3%, Zn: 0 to 1.0%, the balance Cu and unavoidable impurities The product plate material is subjected to cold rolling with a work roll having a roll diameter of 70 mm or more and a final rolling reduction ratio of 4 to 15%, and a total rolling ratio of 20 to 80% (finishing cold rolling process),
The plate after the finish cold rolling step, after heating at 5N / mm 2 or more 30 N / mm 2 lower than the temperature range of 250 to 550 ° C. while applying tension to room temperature at less than the maximum cooling rate 100 ° C. / sec Cooling process (low temperature annealing process),
The manufacturing method of the copper alloy board | plate material which has this.
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015034336A (en) * | 2013-07-11 | 2015-02-19 | 古河電気工業株式会社 | Copper alloy sheet material and production method thereof |
-
2015
- 2015-03-23 JP JP2015059909A patent/JP6533402B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015034336A (en) * | 2013-07-11 | 2015-02-19 | 古河電気工業株式会社 | Copper alloy sheet material and production method thereof |
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CN113774250B (en) * | 2021-09-24 | 2024-05-10 | 佛山市顺德区精艺万希铜业有限公司 | High-strength high-heat-conductivity high-corrosion-resistance copper alloy and preparation method thereof |
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