JP2013108122A - Copper alloy sheet excellent in heat radiating property and repeated bending workability - Google Patents
Copper alloy sheet excellent in heat radiating property and repeated bending workability Download PDFInfo
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本発明は、照明用などのＬＥＤ実装基板をはじめとするフレキシブルプリント基板（ＦＰＣ）として好適な銅合金板、特に放熱性及び繰返し曲げ加工性に優れた銅合金板、ならびにこれを用いた電子機器部品等に関する。 The present invention relates to a copper alloy plate suitable as a flexible printed circuit board (FPC) including an LED mounting substrate for illumination and the like, particularly a copper alloy plate excellent in heat dissipation and repetitive bending workability, and an electronic apparatus using the same Regarding parts.
ＬＥＤ照明は、従来の白熱電球や蛍光灯などと比較して低消費電力、長寿命、高速応答性等の長所を有し、製品価格の低下と共に、急速に普及が進んでおり、室内用照明に加えて、液晶テレビや液晶モニターなどのバックライト、自動車の照明用など、各種用途も広がっている。 LED lighting has advantages such as low power consumption, long life, and high-speed response compared to conventional incandescent bulbs and fluorescent lamps, etc., and it is rapidly spreading as product prices decrease. In addition, various applications such as backlights for LCD TVs and LCD monitors, and lighting for automobiles are also expanding.
ＬＥＤ自体は半導体であるため、定格範囲内での使用では発光素子自身は長寿命であるが、発光素子を覆う樹脂材料は熱により劣化しやすく、発熱により容易に透明度が低下して照明用の使用に適さなくなる。また、ＬＥＤは、発光特性や放熱性に配慮して、種々のパッケージ形状のものが製造されているが、小さなスペースで使用する場合には、省スペース化や成形方法など、様々な工夫が必要である。 Since the LED itself is a semiconductor, the light emitting element itself has a long life when used within the rated range. However, the resin material covering the light emitting element is easily deteriorated by heat, and the transparency is easily lowered by heat generation. Unsuitable for use. In addition, LEDs are manufactured in various package shapes in consideration of light emission characteristics and heat dissipation. However, when used in a small space, various devices such as space saving and molding methods are required. It is.
発熱の問題への対応として、ＦＰＣから効率良く放熱するため、ＦＰＣに放熱板を張り合わせることが提案されており、また、省スペース化については、ＦＰＣ上にＬＥＤを配置することが試みられている（特許文献１）。 In order to deal with the problem of heat generation, in order to efficiently dissipate heat from the FPC, it has been proposed to attach a heat sink to the FPC, and for space saving, an attempt has been made to place an LED on the FPC. (Patent Document 1).
また、照明装置として、ＬＥＤを配置した回路基板に複雑な加工を行い、立体成形を行うことも提案されている（特許文献２）。 In addition, as a lighting device, it has been proposed to perform complicated processing on a circuit board on which LEDs are arranged to perform three-dimensional molding (Patent Document 2).
ＬＥＤをＦＰＣ上に実装した場合、基板である樹脂の放熱性が十分でないため、長時間の使用で発光素子を覆う樹脂が熱劣化し、照明としての寿命が短くなってしまう。
発熱への対応として、ＦＰＣに放熱板としてアルミニウム板を張り合わせた場合、ＦＰＣの回路を構成している銅配線との線熱膨張係数の違いにより、ＦＰＣ回路にそりが生じるという問題がある。さらに、熱による膨張、収縮を繰り返すことで、ＦＰＣの銅配線が繰返し引張り応力を受け、破断に至ることもある。
放熱板として銅板を用いた場合には上記問題は発生しないが、銅はアルミニウムよりも加工硬化係数が大きいため、複雑な形状にＦＰＣを成型する際に、曲げ部にクラックが発生し易い。クラックが発生すると、これを車載などの繰返し振動が加わる環境下で使用する場合、クラックが進展して破断に至るなどの問題が生じる。
本発明は上記の課題を解決するためになされたものであり、放熱性、繰返し曲げ加工性、及び、形状維持性に優れた銅合金板を提供することを課題とする。
When the LED is mounted on the FPC, the heat dissipation of the resin that is the substrate is not sufficient, so that the resin that covers the light emitting element is deteriorated by heat for a long time, and the lifetime as illumination is shortened.
As a countermeasure to heat generation, when an aluminum plate is bonded to the FPC as a heat dissipation plate, there is a problem that warpage occurs in the FPC circuit due to a difference in linear thermal expansion coefficient from the copper wiring constituting the FPC circuit. Furthermore, by repeating expansion and contraction due to heat, the copper wiring of the FPC repeatedly receives tensile stress and may break.
When a copper plate is used as the heat radiating plate, the above problem does not occur. However, since copper has a larger work hardening coefficient than aluminum, cracks are likely to occur in the bent portion when FPC is molded into a complicated shape. When a crack occurs, when it is used in an environment where repeated vibration is applied, such as in-vehicle, a problem such as the crack progressing and breaking occurs.
This invention is made | formed in order to solve said subject, and makes it a subject to provide the copper alloy plate excellent in heat dissipation, repeated bending workability, and shape maintenance property.
本発明者は上記課題を解決するために研究を重ねたところ、銅合金板の表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られた所定位置の結晶方位の集積度を制御することで、繰返し曲げ加工性等を向上させることができることを見出した。 The present inventor has conducted research to solve the above-mentioned problems, and has obtained a predetermined position obtained by performing equal area division used for display by the vector method on the stereo triangle in the normal direction of the surface of the copper alloy plate. It has been found that repeated bending workability and the like can be improved by controlling the degree of integration of the crystal orientation.
以上の知見を背景にして完成した本発明は一側面において、Ａｇを０〜１．０質量％、Ｔｉを０〜０．０８質量％、Ｎｉを０〜２．０質量％、Ｚｎを０〜３．５質量％、Ｃｒ、Ｆｅ、Ｉｎ、Ｐ、Ｓｉ、Ｓｎ、及びＺｒの群から選択された一種以上を合計で０〜０．５質量％含有し、残部Ｃｕ及び不純物からなり、導電率が６０％ＩＡＣＳ以上であり、引張強さが３５０ＭＰａ以上であり、板表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られたボックス番号１の結晶方位の集積度が１以上である銅合金板である。
In one aspect, the present invention completed with the above knowledge in the background, Ag is 0 to 1.0 mass%, Ti is 0 to 0.08 mass%, Ni is 0 to 2.0 mass%, and Zn is 0 to 0 mass%. 3.5% by mass, containing 0 to 0.5% by mass in total of at least one selected from the group consisting of Cr, Fe, In, P, Si, Sn, and Zr, comprising the balance Cu and impurities, and having conductivity Is a crystal of
本発明に係る銅合金板は一実施形態において、Ａｇ、Ｔｉ、Ｎｉ、Ｚｎ、Ｃｒ、Ｆｅ、Ｉｎ、Ｐ、Ｓｉ、Ｓｎ及びＺｒからなる群から選択された一種以上を合計で０．０１質量％以上含有する。 In one embodiment, the copper alloy sheet according to the present invention is 0.01 mass in total of at least one selected from the group consisting of Ag, Ti, Ni, Zn, Cr, Fe, In, P, Si, Sn, and Zr. % Or more.
本発明に係る銅合金板は別の一実施形態において、前記ボックス番号１の結晶方位の集積度が５以下である。
In another embodiment of the copper alloy plate according to the present invention, the accumulation degree of the crystal orientation of the
本発明に係る銅合金板は一実施形態において、引張り強さが２００℃で３０分間加熱後に２５０ＭＰａ以上である。 In one embodiment, the copper alloy plate according to the present invention has a tensile strength of 250 MPa or more after heating at 200 ° C. for 30 minutes.
本発明に係る銅合金板は別の一実施形態において、ＦＰＣ基板用である。 In another embodiment, the copper alloy plate according to the present invention is for an FPC board.
本発明に係る銅合金板は更に別の一実施形態において、ＬＥＤ照明を実装したＦＰＣ基板用である。 In yet another embodiment, the copper alloy plate according to the present invention is for an FPC board on which LED lighting is mounted.
本発明に係る銅合金板は更に別の一実施形態において、厚みが０．０５〜０．３ｍｍである。 In yet another embodiment, the copper alloy plate according to the present invention has a thickness of 0.05 to 0.3 mm.
本発明は別の一側面において、本発明の銅合金板を用いた電子機器部品である。 Another aspect of the present invention is an electronic device component using the copper alloy plate of the present invention.
本発明は更に別の一側面において、本発明の銅合金板を用いたＬＥＤ照明を実装したＦＰＣである。 In still another aspect, the present invention is an FPC in which LED lighting using the copper alloy plate of the present invention is mounted.
本発明によれば、放熱性、繰返し曲げ加工性、及び、形状維持性に優れた銅合金板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the copper alloy plate excellent in heat dissipation, repeated bending workability, and shape maintainability can be provided.
（銅箔の成分）
本発明の銅合金板は、Ａｇを０〜１．０質量％、Ｔｉを０〜０．０８質量％、Ｎｉを０〜２．０質量％、Ｚｎを０〜３．５質量％、Ｃｒ、Ｆｅ、Ｉｎ、Ｐ、Ｓｉ、Ｓｎ及びＺｒの群から選択された一種以上を合計で０〜０．５質量％含有し、残部Ｃｕ及び不純物からなる。
Ａｇは添加による導電率の低下の影響が小さいため、特に制限はないが、添加濃度が高くなると共にコストが増加するため、１．０質量％以下とする。
添加による導電率低下の影響が大きいＣｒ、Ｆｅ、Ｉｎ、Ｐ、Ｓｉ、Ｓｎ、Ｚｒは、これら元素の合計につき、０．５質量％以下、また、特に影響が大きいＴｉは、０．０８質量％以下とする。また、Ｎｉは２．０質量％以下、Ｚｎは３．５質量％以下とする。
銅箔の耐熱性を改善するために、銅にＡｇ、Ｃｒ、Ｆｅ、Ｉｎ、Ｎｉ、Ｐ、Ｓｉ、Ｓｎ、Ｔｉ、Ｚｎ及びＺｒからなる群から選択された一種以上を合計で０．０１質量％以上添加してもよい。添加元素の合計濃度が０．０１質量％を下回ると、添加元素の効果が発現せず耐熱性が不足するおそれがある。
(Copper foil components)
The copper alloy sheet of the present invention is composed of 0 to 1.0 mass% Ag, 0 to 0.08 mass% Ti, 0 to 2.0 mass% Ni, 0 to 3.5 mass% Zn, Cr, One or more selected from the group consisting of Fe, In, P, Si, Sn and Zr is contained in a total amount of 0 to 0.5% by mass, and the balance is Cu and impurities.
Ag is not particularly limited since the effect of the decrease in conductivity due to the addition is small, but it is 1.0% by mass or less because the addition concentration increases and the cost increases.
Cr, Fe, In, P, Si, Sn, and Zr, which have a large effect on the decrease in conductivity due to the addition, are 0.5% by mass or less with respect to the total of these elements. % Or less. Ni is 2.0% by mass or less, and Zn is 3.5% by mass or less.
In order to improve the heat resistance of the copper foil, a total of 0.01 mass of one or more selected from the group consisting of Ag, Cr, Fe, In, Ni, P, Si, Sn, Ti, Zn and Zr is added to copper. % Or more may be added. When the total concentration of the additive elements is less than 0.01% by mass, the effects of the additive elements are not exhibited and the heat resistance may be insufficient.
合金元素添加のベースのＣｕとしてはＪＩＳ−Ｃ１０２０に規格する無酸素銅又はＪＩＳ−Ｃ１１００に規格するタフピッチ銅が適する。酸素濃度は、タフピッチ銅溶湯では０．０１〜０．０５質量％、無酸素銅溶湯では０．００１質量％以下が通常である。
Ｃｕと比較し酸化しやすいＣｒ、Ｆｅ、Ｉｎ、Ｎｉ、Ｐ、Ｓｉ、Ｓｎ、Ｔｉ、Ｚｎ及びＺｒは、無酸素銅溶湯中に添加するのが一般的である。酸素を含有する溶銅にＰ、Ｓｉ等の脱酸剤を添加して酸素濃度を１０ｐｐｍ以下に下げた後、これら合金元素を添加しても良い。ＡｇはＣｕより酸化し難いので、タフピッチ銅溶湯中、無酸素銅溶湯中ともに添加できる。
As the base Cu added with the alloy element, oxygen-free copper standardized to JIS-C1020 or tough pitch copper standardized to JIS-C1100 is suitable. The oxygen concentration is usually 0.01 to 0.05% by mass for a tough pitch copper melt and 0.001% by mass or less for an oxygen free copper melt.
In general, Cr, Fe, In, Ni, P, Si, Sn, Ti, Zn, and Zr, which are easily oxidized as compared with Cu, are added to the oxygen-free copper melt. After adding a deoxidizer such as P or Si to the molten copper containing oxygen to reduce the oxygen concentration to 10 ppm or less, these alloy elements may be added. Since Ag is harder to oxidize than Cu, it can be added to both the tough pitch copper melt and the oxygen free copper melt.
（放熱性）
加熱された材料を放熱するには、熱伝導が良い材料が求められる。熱伝導は、材料の導電率が高いものが良い。ＬＥＤ照明点灯時の発熱を考えると、ＬＥＤの実装密度や照明装置の形状などの影響要因もあるが、導電率が６０％ＩＡＣＳ以上であればよく、７０％ＩＡＣＳ以上であればより好ましい。
(Heat dissipation)
In order to dissipate the heated material, a material having good heat conduction is required. The heat conduction is preferably a material having a high electrical conductivity. Considering the heat generated when the LED lighting is turned on, there are influential factors such as the LED mounting density and the shape of the lighting device, but the conductivity may be 60% IACS or more, and more preferably 70% IACS or more.
（繰返し曲げ加工性）
繰返し曲げ加工性について、集合組織との関係を調べたところ、理由は定かではないが、銅合金板の表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られた所定位置の結晶方位の集積度と相関が見られた。具体的には、銅合金板表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られたボックス番号１の結晶方位の集積度が１以上であればよく、２．５以上であればより好ましい。
図１は、銅合金の結晶方位を表すベクトル法の回転角のステレオ投影図表示である。図１において、銅合金板表面の法線方向（ＮＤ）を表す点ＮＤは、それが載っているステレオ三角（Ｔ１）上の座標（ψ、ω）で示されている。このステレオ三角を、等面積分割（Ruerらによる）で３６個に区分したものが図２である。この図２のステレオ三角における結晶方位のうち、番号１で示された領域にあるものが「ボックス番号１の結晶方位」である（古林、「再結晶と材料組織」、第１版、内田老鶴圃、第８８〜８９頁参照）。また、「ボックス番号１の結晶方位の集積度」は、ボックス番号１に相当する方位で表される極点図上の区画の平均強度を表す。
(Repeated bending workability)
When the relationship with the texture of the repeated bending workability was investigated, the reason is not clear, but the equal area division used in the display by the vector method was performed on the stereo triangle in the normal direction of the surface of the copper alloy plate. Correlation was found with the degree of crystal orientation accumulation at the predetermined position. Specifically, if the degree of integration of the crystal orientation of
FIG. 1 is a stereo projection diagram representation of the rotation angle of the vector method representing the crystal orientation of a copper alloy. In FIG. 1, a point ND representing the normal direction (ND) of the copper alloy plate surface is indicated by coordinates (ψ, ω) on the stereo triangle (T1) on which the point is placed. FIG. 2 shows this stereo triangle divided into 36 by equal area division (by Ruer et al.). Among the crystal orientations in the stereo triangle of FIG. 2, those in the region indicated by
（形状維持性）
材料を所定の形状に成形した後、初期の加工形状を維持するには、ある程度の材料強度が必要である。加工形状の構造などの影響要因もあるが、材料強度である引張強さが３５０ＭＰａ未満の場合には、材料に加わる力で容易に変形する。このため、引張強さは３５０ＭＰａ以上である必要がある。強度の上限については特に設定しないが、材料の加工度を上げることで強度を高くした場合には、一般に曲げ加工性が劣化することが知られており、従って、曲げ加工性とのバランスを考慮して材料を加工すれば良い。また、引張強さは４００ＭＰａ以上であるのがより好ましい。
(Shape maintenance)
After the material is formed into a predetermined shape, a certain level of material strength is required to maintain the initial processed shape. Although there are influential factors such as the structure of the processed shape, when the tensile strength, which is the material strength, is less than 350 MPa, it is easily deformed by the force applied to the material. For this reason, the tensile strength needs to be 350 MPa or more. The upper limit of strength is not particularly set, but it is generally known that when the strength is increased by increasing the workability of the material, bending workability is generally deteriorated. Therefore, the balance with bending workability is considered. Then, the material can be processed. Further, the tensile strength is more preferably 400 MPa or more.
（耐熱性）
耐熱性については、ＬＥＤ照明の特性から、照明機器として長時間使用できるよう、通常は１５０℃未満の温度で使用されるように設計される。軟化した場合には初期の加工形状を維持することができないため、耐熱性を確保することは重要である。一方、照明機器としては数万時間程度の使用が想定されるが、これをそのまま再現する長時間の加熱試験は現実的ではないため、目安として、実使用条件よりも高温で短時間、ここでは２００℃で３０分間保持する条件で加熱し、引張強さ２５０ＭＰａ以上の場合に耐熱性が良好と判断した。また、２００℃で３０分間加熱後に３００ＭＰａ以上を維持するのがより好ましい。なお、耐熱性は結晶方位の集積度との相関が見られ、銅合金板表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られたボックス番号１の結晶方位の集積度が５を超えると耐熱性が不良となることがある。このため、当該ボックス番号１の結晶方位の集積度は５以下であるのが好ましい。
(Heat-resistant)
About heat resistance, from the characteristic of LED lighting, it is designed so that it may be normally used at the temperature of less than 150 degreeC so that it can be used as lighting equipment for a long time. It is important to ensure heat resistance because the initial processed shape cannot be maintained when softened. On the other hand, it is assumed that the lighting equipment will be used for several tens of thousands of hours, but a long-time heating test that reproduces this as it is is not realistic. Heating was carried out at 200 ° C. for 30 minutes, and when the tensile strength was 250 MPa or more, it was judged that the heat resistance was good. Moreover, it is more preferable to maintain 300 MPa or more after heating at 200 ° C. for 30 minutes. In addition, the heat resistance has a correlation with the degree of integration of crystal orientation, and
本発明に係る銅合金板の厚みは、０．０５〜０．３ｍｍであるのが好ましい。銅合金板の厚みが０．０５ｍｍ未満であると材料が薄いために形状を維持するのが困難という問題が生じることがあり、０．３ｍｍ超であると材料が厚すぎるために製品の重量が重くなりすぎるという問題が生じることがある。また、このように、本発明に係る銅合金板は銅箔の形態も含んでいる。 The thickness of the copper alloy plate according to the present invention is preferably 0.05 to 0.3 mm. If the thickness of the copper alloy plate is less than 0.05 mm, the material may be thin, which may make it difficult to maintain the shape. The problem of becoming too heavy can occur. In addition, as described above, the copper alloy plate according to the present invention includes a form of copper foil.
銅合金板の成分、形状維持性及び結晶方位の集積度が上記の特性範囲にあれば、製造条件によらず、本発明の効果は発現する。本発明の銅合金板は、例えば、次のようなプロセスによって製造することができる。 The effects of the present invention are manifested regardless of the manufacturing conditions as long as the components, shape retention, and crystal orientation integration degree of the copper alloy plate are within the above-mentioned characteristic ranges. The copper alloy plate of the present invention can be manufactured, for example, by the following process.
圧延銅箔の製造プロセスは、電気銅を純銅の原料に使用し、必要に応じて合金元素を添加した後、鋳造して厚み１００〜３００ｍｍのインゴットを製造する。このインゴットを熱間圧延して厚み５〜２０ｍｍ程度とした後、冷間圧延と焼鈍を繰り返して、冷間圧延で所定の厚みに仕上げる。
先述の形状維持性及び結晶方位の集積度を満たす銅箔は、最終再結晶焼鈍の昇温速度、ならびに最終再結晶焼鈍の直後に行われる最終冷間圧延の加工条件である総加工度、及び、１パス目の加工度を調整することで得られる。ここで、最終再結晶焼鈍とは、製品の厚みまで加工する最終冷間圧延の前の再結晶焼鈍である。また、最終冷間圧延では、一対のロール間に材料を繰返し通過させ（以下「パス」とする）、厚みを仕上げていく。ここで、１パス目とは、最終再結晶焼鈍後の材料を製品の厚みに仕上げる最終冷間圧延における最初のパスを示す。
最終再結晶焼鈍の昇温速度は１２〜５０℃／ｓであれば良い。昇温速度が１２℃／ｓ未満である場合、及び、５０℃／ｓ超である場合は、先述の繰返し曲げ加工性を満たすことが困難である。
最終冷間圧延の総加工度の上限値は特に限定はされない。最終冷間圧延の総加工度は一般的には８５％以下である。加工度は、圧延前と圧延後との厚みの差を圧延前の厚みで除した値を百分率で表したものである。また、総加工度の下限値については、合金成分や濃度により異なり、引張強さの下限値を超えるように設定すれば良い。例えば、Ｓｎを０．１２質量％含む銅箔については、最終冷間圧延の総加工度は５０％以上であればよく、６０％以上であればより好ましい。
最終冷間圧延の１パス目の加工度は２０％以下であれば良い。最終冷間圧延の１パス目の加工度が２０％を超える場合は、本発明に係る結晶方位の集積度の規定を満たすことができず、先述の繰り返し曲げ加工性を満たすことが困難である。
The manufacturing process of a rolled copper foil uses electrolytic copper as a raw material for pure copper, adds an alloying element as necessary, and casts to produce an ingot having a thickness of 100 to 300 mm. This ingot is hot-rolled to a thickness of about 5 to 20 mm, and then cold-rolling and annealing are repeated to finish it to a predetermined thickness by cold-rolling.
The copper foil that satisfies the shape maintenance property and the degree of crystal orientation integration described above is the temperature increase rate of the final recrystallization annealing, and the total workability that is the processing conditions of the final cold rolling performed immediately after the final recrystallization annealing, and It is obtained by adjusting the processing degree of the first pass. Here, the final recrystallization annealing is a recrystallization annealing before the final cold rolling for processing to the thickness of the product. In the final cold rolling, the material is repeatedly passed between a pair of rolls (hereinafter referred to as “pass”) to finish the thickness. Here, the first pass indicates the first pass in the final cold rolling in which the material after the final recrystallization annealing is finished to the product thickness.
The temperature increase rate of the final recrystallization annealing may be 12 to 50 ° C./s. When the rate of temperature increase is less than 12 ° C./s and when it exceeds 50 ° C./s, it is difficult to satisfy the above-described repeated bending workability.
The upper limit value of the total workability of the final cold rolling is not particularly limited. The total degree of work in final cold rolling is generally 85% or less. The degree of work is a percentage obtained by dividing the difference in thickness between before and after rolling by the thickness before rolling. Further, the lower limit value of the total workability varies depending on the alloy components and the concentration, and may be set so as to exceed the lower limit value of the tensile strength. For example, for a copper foil containing 0.12% by mass of Sn, the total degree of work in the final cold rolling may be 50% or more, and more preferably 60% or more.
The degree of processing in the first pass of the final cold rolling may be 20% or less. When the degree of workability in the first pass of final cold rolling exceeds 20%, it is difficult to satisfy the provision of the degree of crystal orientation accumulation according to the present invention, and it is difficult to satisfy the above-described repeated bending workability. .
本発明の銅合金板は、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機器部品等に使用することができる。また、特に、本発明の銅合金板は、ＬＥＤ照明を実装したＦＰＣの材料として好適である。 The copper alloy plate of the present invention can be used for electronic device parts such as lead frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries. In particular, the copper alloy plate of the present invention is suitable as an FPC material on which LED lighting is mounted.
以下に本発明の実施例を示すが、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。 Examples of the present invention are shown below, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
［圧延銅箔の製造］
表１に記載の各種銅母材に、表１に記載の各種元素を添加し、厚み１００ｍｍのインゴットを鋳造した。次に、インゴットを熱間圧延にて５ｍｍまで圧延し、酸化スケールを除去した後、冷間圧延と焼鈍を繰り返し、最終冷間圧延にて表１に記載の条件で０．０５〜０．３ｍｍまで圧延した。なお、最終冷間圧延の直前に最終再結晶焼鈍を行った。最終再結晶焼鈍は表１に記載の昇温速度で、材料温度が最高で５００℃となるよう加熱し、室温（２５℃）から５００℃まで到達する時間から、昇温速度を算出した。そして、材料温度が５００℃に到達後、直ちに冷却を行った。
[Manufacture of rolled copper foil]
Various elements described in Table 1 were added to various copper base materials described in Table 1 to cast an ingot having a thickness of 100 mm. Next, the ingot is rolled to 5 mm by hot rolling, the oxide scale is removed, then cold rolling and annealing are repeated, and 0.05 to 0.3 mm under the conditions described in Table 1 by final cold rolling. Rolled to. The final recrystallization annealing was performed immediately before the final cold rolling. The final recrystallization annealing was performed at the rate of temperature increase shown in Table 1, and the material temperature was heated to 500 ° C. at maximum, and the rate of temperature increase was calculated from the time required to reach 500 ° C. from room temperature (25 ° C.). And it cooled immediately after material temperature reached | attained 500 degreeC.
［形状維持性］
ＪＩＳ Ｚ ２２４１に準じて、圧延平行方向が長手方向となるように採取したＪＩＳ１３Ｂ号試験片を供試材とし、引張り試験により引張強さを求めた。引張り試験では、ＯＲＩＥＮＴＥＣ社製のＵＴＭ−１０Ｔを用い、引張り速度５ｍｍ／分にて、同一試料につきｎ＝２で測定した平均値を測定値とした。引張強さが３５０ＭＰａ以上のとき、形状維持性を○とし、引張強さが３５０ＭＰａ未満のとき、形状維持性を×と評価した。
[Shape maintenance]
In accordance with JIS Z 2241, a JIS No. 13B test piece collected so that the rolling parallel direction was the longitudinal direction was used as a test material, and the tensile strength was obtained by a tensile test. In the tensile test, UTM-10T manufactured by ORIENTEC Co., Ltd. was used, and the average value measured at n = 2 for the same sample at a tensile speed of 5 mm / min was used as the measured value. When the tensile strength was 350 MPa or more, the shape maintaining property was evaluated as ◯, and when the tensile strength was less than 350 MPa, the shape maintaining property was evaluated as x.
［放熱性］
最終冷間圧延後の板厚にて、ＪＩＳ Ｈ ０５０５に準拠した四端子法により測定した導電率（％ＩＡＣＳ）にて評価した。
[Heat dissipation]
The plate thickness after the final cold rolling was evaluated by the conductivity (% IACS) measured by the four-terminal method based on JIS H 0505.
［集積度］
２０ｍｍ四方に切り出した試料を、温度２００℃の加熱炉で３０分間保持し、次に、加熱炉から取り出して大気中（室温）に放置して冷却した後、集積度測定に供した。２００℃で３０分加熱することは、ＦＰＣを製造する際、銅箔に樹脂を積層する工程の処理温度を模擬したものである。板表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られたボックス番号１の結晶方位の集積度を評価した。具体的には、まず、株式会社リガク製Ｘ線回折装置RINT-2000を用いて、極点図測定を行った。次に、測定したデータについて、株式会社リガク製ソフトウェアPole Figure Data Processingを用いて極点図化し、株式会社ノルム工学製Standard ODF及びInverse Dispを用いて図２の分割を行い、集積度を評価した。
[Accumulation degree]
A sample cut out in a 20 mm square was held in a heating furnace at a temperature of 200 ° C. for 30 minutes, then taken out from the heating furnace, allowed to cool in the atmosphere (room temperature), and then subjected to integration measurement. Heating at 200 ° C. for 30 minutes simulates the processing temperature of the step of laminating the resin on the copper foil when manufacturing the FPC. The degree of integration of the crystal orientation of
［耐熱性］
上記のＪＩＳ１３Ｂ号試験片を用い、これを加熱炉に入れて温度が２００℃に達した後に３０分間保持して試料を取り出し、空冷して引張り試験に供した。引張り試験は、上記と同じ条件で実施した。引張強さ２５０ＭＰａ以上の場合を耐熱性が良好（○）と判断し、引張強さ２５０ＭＰａ未満の場合を耐熱性が不良（×）と判断した。
[Heat-resistant]
Using the above JIS13B test piece, the sample was put in a heating furnace and, after the temperature reached 200 ° C., held for 30 minutes, the sample was taken out, air-cooled, and subjected to a tensile test. The tensile test was performed under the same conditions as described above. When the tensile strength was 250 MPa or more, the heat resistance was judged as good (◯), and when the tensile strength was less than 250 MPa, the heat resistance was judged as poor (x).
［繰返し曲げ加工性］
以下の手順で、繰返し曲げ加工性を評価した。
（１）圧延平行方向および直角方向につき、長さ５０ｍｍ×幅１０ｍｍに試料を切り出し、２００℃で３０分加熱した後に空冷し、繰り返し曲げ性評価材として供した。
（２）曲げＲ＝０．５ｍｍにて、９０°にＶ曲げ加工し、これを元の短冊状に曲げ戻した後、９０°Ｖ曲げ加工と曲げ戻しを繰り返した。
（３）上記操作を繰り返して、１回毎に９０°Ｖ曲げした時の曲げ加工部を５０倍に拡大観察し、クラックまたは破断発生の有無を確認した。そして、クラックまたは破断が発生しない最大曲げ回数を調査した。クラックが発生しない最大曲げ回数が５回以上を「◎」、４回を「○」、３回を「△」、３回未満を「×」として評価した。
表１に評価条件及び結果を示す。
[Repeated bending workability]
Repeated bending workability was evaluated by the following procedure.
(1) A sample was cut into a length of 50 mm and a width of 10 mm in the rolling parallel direction and the perpendicular direction, heated at 200 ° C. for 30 minutes, air-cooled, and repeatedly used as a bendability evaluation material.
(2) V-bending was performed at 90 ° at a bending R = 0.5 mm, and this was bent back to the original strip shape, and then 90 ° V bending and bending back were repeated.
(3) The above operation was repeated, and the bent portion when bent 90 ° V every time was magnified 50 times to confirm whether cracks or breakage occurred. Then, the maximum number of bendings at which cracks or breakage did not occur was investigated. The maximum number of bendings at which cracks did not occur was evaluated as “」 ”for 4 times or more,“ ◯ ”for 4 times,“ Δ ”for 3 times, and“ x ”for less than 3 times.
Table 1 shows the evaluation conditions and results.
実施例１〜３６は、いずれも各元素の濃度が本発明で規定する上限値以下であり、導電率が６０％ＩＡＣＳ以上、引張強さが３５０ＭＰａ以上、板表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られたボックス番号１の結晶方位の集積度が１以上であることから、いずれも形状維持性、放熱性（導電率）、及び、繰返し曲げ加工性に優れていた。
特に実施例１〜３４は、Ａｇ、Ｔｉ、Ｎｉ、Ｚｎ、Ｃｒ、Ｆｅ、Ｉｎ、Ｐ、Ｓｉ、Ｓｎ及びＺｒからなる群から選択された一種以上を合計で０．０１質量％以上含有しており、耐熱性にも優れていた。
比較例１は、添加元素濃度が高すぎるため、導電率が低くて放熱性が悪かった。
比較例２及び６は、最終冷間圧延における１パス目の加工度が２０％を超えているため、結晶方位の集積度の規定を満たしておらず、繰返し曲げ加工性が悪かった。
比較例３は、最終再結晶焼鈍における昇温速度が１２℃／ｓ未満となっているいため、結晶方位の集積度の規定を満たしておらず、繰返し曲げ加工性が悪かった。
比較例４は、最終再結晶焼鈍における昇温速度が５０℃／ｓを超えているため、結晶方位の集積度の規定を満たしておらず、繰返し曲げ加工性が悪かった。
比較例５は、最終冷間圧延における圧延総加工度が低すぎるため、引張り強さが３５０ＭＰａ未満となっており、形状維持性が悪かった。
In each of Examples 1 to 36, the concentration of each element is less than or equal to the upper limit defined in the present invention, the conductivity is 60% IACS or more, the tensile strength is 350 MPa or more, and the plate surface has a stereo triangle in the normal direction. On the other hand, since the degree of integration of the crystal orientation of
Especially Examples 1-34 contain 0.01 mass% or more in total of 1 or more types selected from the group which consists of Ag, Ti, Ni, Zn, Cr, Fe, In, P, Si, Sn, and Zr. And excellent heat resistance.
In Comparative Example 1, since the additive element concentration was too high, the conductivity was low and the heat dissipation was poor.
In Comparative Examples 2 and 6, the workability of the first pass in the final cold rolling exceeded 20%, so the regulation of the degree of crystal orientation was not satisfied, and the repeated bending workability was poor.
In Comparative Example 3, since the rate of temperature increase in the final recrystallization annealing was less than 12 ° C./s, the regulation of the degree of integration of crystal orientation was not satisfied, and the repeated bending workability was poor.
In Comparative Example 4, the rate of temperature increase in the final recrystallization annealing exceeded 50 ° C./s, so the regulation of the degree of integration of crystal orientation was not satisfied, and the repeated bending workability was poor.
In Comparative Example 5, since the total degree of rolling in the final cold rolling was too low, the tensile strength was less than 350 MPa, and the shape maintainability was poor.
Claims (9)
導電率が６０％ＩＡＣＳ以上であり、
引張強さが３５０ＭＰａ以上であり、
板表面の法線方向のステレオ三角に対し、ベクトル法による表示で用いられる等面積分割を行って得られたボックス番号１の結晶方位の集積度が１以上である銅合金板。 Ag is 0 to 1.0 mass%, Ti is 0 to 0.08 mass%, Ni is 0 to 2.0 mass%, Zn is 0 to 3.5 mass%, Cr, Fe, In, P, Si, One or more selected from the group of Sn and Zr is contained in a total of 0 to 0.5% by mass, and the balance is Cu and impurities,
Conductivity is 60% IACS or higher,
The tensile strength is 350 MPa or more,
A copper alloy plate having a degree of integration of crystal orientations of box number 1 obtained by performing equal area division used for display by a vector method with respect to a stereo triangle in the normal direction of the plate surface.
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| JP2014040647A (en) * | 2012-08-23 | 2014-03-06 | Jx Nippon Mining & Metals Corp | Copper alloy plate excellent in heat release property and processability in repeated bending |
| JP2014058704A (en) * | 2012-09-14 | 2014-04-03 | Jx Nippon Mining & Metals Corp | Rolled copper foil |
| JP2014058705A (en) * | 2012-09-14 | 2014-04-03 | Jx Nippon Mining & Metals Corp | Rolled copper foil and copper-clad laminate |
| JP2014080680A (en) * | 2012-09-28 | 2014-05-08 | Jx Nippon Mining & Metals Corp | Copper alloy sheet having excellent heat dissipation and repeated bendability |
| JP2014080679A (en) * | 2012-09-28 | 2014-05-08 | Jx Nippon Mining & Metals Corp | Copper alloy sheet having excellent heat dissipation and repeated bendability |
| JP2014080677A (en) * | 2012-09-28 | 2014-05-08 | Jx Nippon Mining & Metals Corp | Copper alloy sheet having excellent heat dissipation and repeated bendability |
| KR101640978B1 (en) * | 2013-06-13 | 2016-07-19 | 제이엑스금속주식회사 | Copper alloy plate having superior conductivity and modulus of bending deflection |
| JP5453565B1 (en) * | 2013-06-13 | 2014-03-26 | Ｊｘ日鉱日石金属株式会社 | Copper alloy sheet with excellent conductivity and bending deflection coefficient |
| KR20140145556A (en) * | 2013-06-13 | 2014-12-23 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Copper alloy plate having superior conductivity and modulus of bending deflection |
| JP2015000990A (en) * | 2013-06-13 | 2015-01-05 | Jx日鉱日石金属株式会社 | Copper alloy sheet excellent in conductivity and deflection coefficient |
| CN103451467A (en) * | 2013-08-15 | 2013-12-18 | 江西理工大学 | High-strength high-conductivity heat-resistant copper alloy |
| KR101786411B1 (en) | 2013-11-08 | 2017-10-17 | 제이엑스금속주식회사 | Copper alloy plate, and electronic part for heat dissipation use which is equipped with same |
| KR101788497B1 (en) | 2013-11-19 | 2017-10-19 | 제이엑스금속주식회사 | Copper alloy plate, and electronic component for large current applications and electronic component for heat dissipation applications each provided with same |
| KR101789956B1 (en) | 2013-11-25 | 2017-10-25 | 제이엑스금속주식회사 | Copper alloy plate having excellent electroconductivity, moldability, and stress relaxation properties |
| JP2016164311A (en) * | 2016-04-05 | 2016-09-08 | Ｊｘ金属株式会社 | Copper alloy sheet excellent in heat releasing property and processability in repeated bending |
| US11473172B2 (en) | 2017-03-24 | 2022-10-18 | Ihi Corporation | Wear-resistant copper-zinc alloy and mechanical device using same |
| RU2709909C1 (en) * | 2018-11-26 | 2019-12-23 | Федеральное государственное автономное образовательное учреждение высшего образования "Белгородский государственный национальный исследовательский университет" (НИУ "БелГУ") | Low-alloyed copper alloy |
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