JP2013191638A - Rolled copper foil for printed wiring board - Google Patents
Rolled copper foil for printed wiring board Download PDFInfo
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- JP2013191638A JP2013191638A JP2012055117A JP2012055117A JP2013191638A JP 2013191638 A JP2013191638 A JP 2013191638A JP 2012055117 A JP2012055117 A JP 2012055117A JP 2012055117 A JP2012055117 A JP 2012055117A JP 2013191638 A JP2013191638 A JP 2013191638A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000011889 copper foil Substances 0.000 title claims abstract description 87
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 238000005096 rolling process Methods 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 2
- 230000037303 wrinkles Effects 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 17
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- 238000001953 recrystallisation Methods 0.000 description 26
- 238000000137 annealing Methods 0.000 description 19
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- 239000004020 conductor Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 238000005098 hot rolling Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Description
本発明は、プリント配線板用の圧延銅箔に関し、とりわけＦＰＣ（Flexible Printed Circuit）用の導電性材料として好適な圧延銅箔に関する。 The present invention relates to a rolled copper foil for printed wiring boards, and more particularly to a rolled copper foil suitable as a conductive material for FPC (Flexible Printed Circuit).
プリント配線板（ＰＷＢ）は、電気絶縁性の材料（絶縁基板）の表面（場合によっては内部にも）に、導電性材料で導体パターンを形成・固着したものを指し、これに電子部品類を搭載し、はんだ付け接続を完了したものがプリント回路板（ＰＣＢ）と呼ばれる。プリント回路板は各種電子機器の制御に欠かせない部品である。 Printed wiring board (PWB) refers to the surface of an electrically insulating material (insulating substrate) (in some cases, also inside), with a conductive pattern formed and secured with a conductive material. A printed circuit board (PCB) that has been mounted and soldered has been completed. The printed circuit board is an indispensable part for controlling various electronic devices.
プリント配線板のベースとなる材料としては一般に銅張積層板が使用される。銅張積層板は合成樹脂ボード、フィルム等の絶縁基板に接着剤を介して、又は接着剤を使用せずに高温高圧下で銅箔を積層接着することにより製造される。 In general, a copper-clad laminate is used as a base material for a printed wiring board. A copper-clad laminate is manufactured by laminating and bonding a copper foil to an insulating substrate such as a synthetic resin board or a film via an adhesive or without using an adhesive under high temperature and pressure.
プリント配線板の内、可動部や屈曲部の配線に多用されるＦＰＣ（Flexible Printed Circuit）では、優れた屈曲疲労特性が要求されることから、電解銅箔に比べて屈曲特性に優れた圧延銅箔を中心として、屈曲特性を向上させる努力がなされてきた。例えば、特開２００１−３２３３５４号公報（特許文献１）や特開２００８−２４８３３１号公報（特許文献２）では、立方体集合組織（（１００）［００１］方位）を発達させることにより、屈曲特性の向上を図っている。 Of the printed wiring boards, FPC (Flexible Printed Circuit), which is frequently used for wiring of movable parts and bent parts, requires excellent bending fatigue characteristics, so rolled copper with superior bending characteristics compared to electrolytic copper foil. Efforts have been made to improve the bending characteristics, centering on foil. For example, in Japanese Patent Application Laid-Open No. 2001-323354 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-248331 (Patent Document 2), by developing a cube texture ((100) [001] orientation), bending characteristics are improved. We are trying to improve.
特開２００９−１５８３８２号公報（特許文献３）では、３００℃の加熱処理を施す前の状態において測定した銅箔の応力−歪み曲線における原点付近の直線的な部分での傾きＢと、前記３００℃の加熱処理を施した後の状態において測定した当該銅箔の応力−歪み曲線における原点付近の直線的な部分での傾きＡとの比Ｂ／Ａを１．２以上から３．０以下に制御することを開示している。 In Japanese Patent Application Laid-Open No. 2009-158382 (Patent Document 3), the slope B at the linear portion near the origin in the stress-strain curve of the copper foil measured before the heat treatment at 300 ° C. The ratio B / A with respect to the slope A in the linear portion near the origin in the stress-strain curve of the copper foil measured in the state after the heat treatment at ℃ was from 1.2 to 3.0 It is disclosed to control.
特開２０１２−００１７８６号公報（特許文献４）では、０度方向（度は銅箔の長さ方向と成す角度、以下同様）のヤング率が８０〜１５０ＧＰａであり、３６０℃×６分間の熱処理を行った後の０度および９０度方向のヤング率が２５〜８０ＧＰａ、該熱処理後の４５度方向のヤング率が８０〜１５０ＧＰａである銅箔を提案し、熱処理後の屈曲疲労特性の向上に加えて、熱処理前にライン張力によって銅箔に折れが発生するのを防止している。 In JP 2012-001786 A (Patent Document 4), the Young's modulus in the 0 degree direction (degree is the angle formed with the length direction of the copper foil, the same applies hereinafter) is 80 to 150 GPa, and heat treatment at 360 ° C. for 6 minutes. Proposed a copper foil having a Young's modulus in the 0 degree and 90 degree directions of 25 to 80 GPa after the heat treatment and a Young's modulus in the 45 degree direction of 80 to 150 GPa after the heat treatment to improve the bending fatigue properties after the heat treatment. In addition, the copper foil is prevented from being bent by the line tension before the heat treatment.
銅張積層板の製造過程においては、銅箔を絶縁基板に貼り合わせるために加熱処理が施されるところ、この加熱処理によって銅箔が再結晶することが一般的である。銅張積層板の工業的な製造ラインでは、銅箔にテンションを掛けながら絶縁基板との積層を行うが、再結晶前後で銅箔に物性差が生じるため、再結晶前の圧延組織と再結晶組織との境界付近や再結晶後の組織となっている部分でシワが入りやすいという問題があった。特許文献４に記載の圧延銅箔では、加熱処理前にテンションが掛かったときの折れの発生を抑制することも狙っているが、加熱処理前後の物性差に起因するシワの抑制の観点では対策がなされておらず、未だ改善の余地が残されている。 In the manufacturing process of the copper clad laminate, heat treatment is performed to bond the copper foil to the insulating substrate, and the copper foil is generally recrystallized by this heat treatment. In an industrial production line for copper-clad laminates, the copper foil is laminated with an insulating substrate while tension is applied. However, the physical properties of the copper foil differ before and after recrystallization. There was a problem that wrinkles were likely to occur near the boundary with the structure and at the part after recrystallization. The rolled copper foil described in Patent Document 4 also aims to suppress the occurrence of folds when tension is applied before the heat treatment, but it is a countermeasure in terms of suppressing wrinkles due to physical property differences before and after the heat treatment. However, there is still room for improvement.
そこで、本発明の課題は、銅張積層板の製造ラインにおいて、加熱処理前後の物性差に起因してシワが発生しにくい圧延銅箔を提供することを課題とする。また、本発明の更なる課題は、そのような圧延銅箔を備えた銅張積層板を提供することである。 Then, the subject of this invention makes it a subject to provide the rolled copper foil which is hard to generate | occur | produce a wrinkle due to the physical property difference before and behind heat processing in the production line of a copper clad laminated board. Moreover, the further subject of this invention is providing the copper clad laminated board provided with such a rolled copper foil.
本発明者は上記課題を解決するために鋭意検討したところ、圧延銅箔の再結晶前後におけるヤング率の差ΔＥを制御することで、シワの発生が有意に抑制可能であることを見出した。 As a result of intensive studies to solve the above problems, the present inventor has found that wrinkles can be significantly suppressed by controlling the difference ΔE in Young's modulus before and after recrystallization of the rolled copper foil.
本発明は上記知見を基礎として完成したものであり、一側面において、２５℃における圧延方向のヤング率Ｅ１がＥ１＝８０〜１３０ＧＰａであり、３５０℃で１秒間の加熱処理をした後、２５℃における圧延方向のヤング率Ｅ２がＥ２＝６０〜１１０ＧＰａであり、ヤング率Ｅ１とヤング率Ｅ２の差ΔＥ＝Ｅ１−Ｅ２が１２〜３３ＧＰａであるプリント配線板用圧延銅箔である。 The present invention has been completed based on the above findings. In one aspect, the Young's modulus E1 in the rolling direction at 25 ° C. is E1 = 80 to 130 GPa, and after heat treatment at 350 ° C. for 1 second, 25 ° C. The rolled copper foil for printed wiring boards has a Young's modulus E2 in the rolling direction of E2 = 60 to 110 GPa and a difference ΔE = E1−E2 between the Young's modulus E1 and Young's modulus E2 of 12 to 33 GPa.
本発明のプリント配線板用圧延銅箔の一実施形態においては、３５０℃で１秒間の加熱処理をした後の圧延面のＸ線回折で求めた２００回折強度（Ｉ）が、微粉末銅のＸ線回折で求めた２００回折強度（Ｉ0）に対し、１０≦Ｉ／Ｉ0≦３０である。 In one embodiment of the rolled copper foil for a printed wiring board of the present invention, the 200 diffraction intensity (I) obtained by X-ray diffraction of the rolled surface after heat treatment at 350 ° C. for 1 second is a fine powdered copper. For the 200 diffraction intensity (I 0 ) determined by X-ray diffraction, 10 ≦ I / I 0 ≦ 30.
本発明のプリント配線板用圧延銅箔の別の一実施形態においては、２５℃における圧延方向のヤング率Ｅ１がＥ１＝８５〜１２５ＧＰａであり、３５０℃で１秒間の加熱処理をした後、２５℃における圧延方向のヤング率Ｅ２がＥ２＝６５〜１００ＧＰａである。 In another embodiment of the rolled copper foil for printed wiring boards of the present invention, the Young's modulus E1 in the rolling direction at 25 ° C. is E1 = 85 to 125 GPa, and after heat treatment at 350 ° C. for 1 second, 25 The Young's modulus E2 in the rolling direction at ° C. is E2 = 65 to 100 GPa.
本発明のプリント配線板用圧延銅箔の更に別の一実施形態においては、ΔＥが１５〜３０ＧＰａである。 In another embodiment of the rolled copper foil for printed wiring boards of this invention, (DELTA) E is 15-30 GPa.
本発明は別の一側面において、上記プリント配線板用圧延銅箔を備えた銅張積層板である。 In another aspect, the present invention is a copper-clad laminate including the rolled copper foil for a printed wiring board.
本発明は更に別の一側面において、上記銅張積層板を材料とするプリント配線板である。 In yet another aspect, the present invention is a printed wiring board made of the copper clad laminate.
本発明に係る圧延銅箔を用いて銅張積層板を製造することにより、加熱処理に伴うシワの発生が抑制されることから、生産性及び歩留まりの向上が期待できる。 By producing a copper-clad laminate using the rolled copper foil according to the present invention, the generation of wrinkles associated with the heat treatment is suppressed, so that improvement in productivity and yield can be expected.
（１．銅箔の組成）
本発明において使用する銅箔基材は圧延銅箔である。圧延銅箔は、振動が継続的に発生する環境に対応でき、耐屈曲性が高い点で電解銅箔よりも優れている。本発明において、「銅箔」には銅合金箔も含まれるものとする。銅箔の材料としては、特に制限はなく、用途や要求特性に応じて適宜選択すればよい。銅箔中のＣｕ濃度は高導電性確保の理由により９９．８質量％以上であることが好ましく、９９．８５質量％以上であることがより好ましく、９９．９質量％以上であることが更により好ましい。但し、Ｃｕ濃度が高すぎてもコスト増加につながるため、９９．９９９質量％以下が好ましく、９９．９９５質量％以下がより好ましい。銅箔中の酸素濃度は亜酸化銅増加につながり、亜酸化銅によるピンホールの発生につながることから０．０５質量以下であることが好ましく、０．０１質量％以下であることがより好ましく、０．００５質量％以下であることが更により好ましく、例えば０．０００１質量％以上０．０１質量％以下とすることができる。このような条件を満たす銅箔の材料として、例えば、ＪＩＳ−Ｈ３５１０若しくはＪＩＳ−Ｈ３１００に規定される無酸素銅やタフピッチ銅を用いることができる。
(1. Composition of copper foil)
The copper foil base material used in the present invention is a rolled copper foil. Rolled copper foil is superior to electrolytic copper foil in that it can cope with an environment in which vibration continuously occurs and has high bending resistance. In the present invention, “copper foil” includes copper alloy foil. There is no restriction | limiting in particular as a material of copper foil, What is necessary is just to select suitably according to a use or a required characteristic. The Cu concentration in the copper foil is preferably 99.8% by mass or more, more preferably 99.85% by mass or more, and more preferably 99.9% by mass or more for reasons of ensuring high conductivity. Is more preferable. However, even if the Cu concentration is too high, it leads to an increase in cost, so 99.999 mass% or less is preferable, and 99.995 mass% or less is more preferable. The oxygen concentration in the copper foil leads to an increase in cuprous oxide, which leads to the generation of pinholes due to cuprous oxide, preferably 0.05 mass or less, more preferably 0.01 mass% or less, More preferably, it is 0.005 mass% or less, for example, can be 0.0001 mass% or more and 0.01 mass% or less. For example, oxygen-free copper or tough pitch copper defined in JIS-H3510 or JIS-H3100 can be used as a copper foil material satisfying such conditions.
また、ヤング率の制御が容易になることから、タフピッチ銅や無酸素銅に対して、Ｓｎ、Ａｇ、Ｉｎ、Ａｕ、Ｃｒ、Ｚｒ、Ｍｇ、Ｐｄ等の合金元素を添加することもできる。これら元素の含有量が合計で０．０５質量％を超えると強度は更に向上するものの、伸びが低下して加工性が悪化する場合があるので、これらの元素の含有量の合計は０．０５質量％以下とするのが好ましい。より好ましくは上記合金元素の含有量が合計で０．０３質量％以下である。上記合金元素を合計した含有量の下限は特に制限されないが、例えば０．００１質量％を下限とすることができる。含有量が合計で０．００１質量％未満であると、所望の効果を得られなくなる他、含有量が小さいためその含有量を制御することが困難になる場合がある。好ましくは、上記合金元素を合計した量の下限値は０．００３質量％以上、更に好ましくは０．００４質量％以上、最も好ましくは０．００５質量％以上である。 In addition, since Young's modulus can be easily controlled, alloy elements such as Sn, Ag, In, Au, Cr, Zr, Mg, and Pd can be added to tough pitch copper and oxygen-free copper. If the total content of these elements exceeds 0.05% by mass, the strength is further improved, but the elongation may decrease and workability may deteriorate, so the total content of these elements is 0.05. It is preferable to set it as the mass% or less. More preferably, the total content of the alloy elements is 0.03% by mass or less. Although the lower limit of the total content of the alloy elements is not particularly limited, for example, 0.001% by mass can be set as the lower limit. If the total content is less than 0.001% by mass, the desired effect cannot be obtained, and the content may be difficult to control because the content is small. Preferably, the lower limit of the total amount of the alloy elements is 0.003% by mass or more, more preferably 0.004% by mass or more, and most preferably 0.005% by mass or more.
（２．銅箔の厚み）
本発明に用いることのできる圧延銅箔の厚さについては特に制限はなく、プリント配線板用に適した厚さに適宜調節すればよい。ＦＰＣの導電性材料として使用する場合、銅箔を薄肉化した方がより高い屈曲性や耐振動性を得ることができる一方で、薄すぎるとシワが発生し易くなることから、例えば５〜７５μｍ程度とすることができる。ファインパターン形成を目的とする場合には３０μｍ以下、好ましくは２０μｍ以下であり、典型的には５〜２０μｍ程度である。
(2. Thickness of copper foil)
There is no restriction | limiting in particular about the thickness of the rolled copper foil which can be used for this invention, What is necessary is just to adjust suitably to the thickness suitable for printed wiring boards. When used as a conductive material for FPC, it is possible to obtain higher flexibility and vibration resistance when the copper foil is thinned. On the other hand, if it is too thin, wrinkles are likely to occur. Can be about. For the purpose of forming a fine pattern, it is 30 μm or less, preferably 20 μm or less, and typically about 5 to 20 μm.
（３．再結晶前後のヤング率の差ΔＥ）
銅張積層板を製造する際、銅箔と絶縁基板を貼り合わせるための加熱処理が行われ、通常はこのときに銅箔の組織が圧延組織から再結晶組織に変化し、軟化して屈曲特性が向上する。本発明に係る圧延銅箔では、２５℃における圧延方向のヤング率をＥ１とし、３５０℃で１秒間の加熱処理をした後、２５℃における圧延方向のヤング率をＥ２としたとき、ヤング率Ｅ１とヤング率Ｅ２の差ΔＥ＝Ｅ１−Ｅ２が１２〜３３ＧＰａであることが特徴の一つである。３５０℃で１秒間の加熱処理というのは銅箔を絶縁基板に貼り合わせるときの典型的な加熱条件であることから、本発明における熱処理の条件とした。尚、再結晶後のヤング率は熱処理条件に大きく依存し、数秒で熱処理したときと１０秒以上の熱処理時間があったときでは大きく異なる。
(3. Difference in Young's modulus before and after recrystallization ΔE)
When manufacturing a copper-clad laminate, heat treatment is performed to bond the copper foil and the insulating substrate. Usually, at this time, the copper foil structure changes from a rolled structure to a recrystallized structure, which softens and bends. Will improve. In the rolled copper foil according to the present invention, when the Young's modulus in the rolling direction at 25 ° C. is E1, and after heat treatment at 350 ° C. for 1 second, the Young's modulus in the rolling direction at 25 ° C. is E2, the Young's modulus E1 One feature is that the difference ΔE = E1−E2 between the Young's modulus E2 and the Young's modulus E2 is 12 to 33 GPa. The heat treatment at 350 ° C. for 1 second is a typical heating condition when the copper foil is bonded to the insulating substrate, and is therefore the heat treatment condition in the present invention. The Young's modulus after recrystallization greatly depends on the heat treatment conditions, and is greatly different between the heat treatment in several seconds and the heat treatment time of 10 seconds or more.
銅張積層板の製造ラインにおいては、途中の熱処理のために、銅箔は再結晶組織と再結晶前の圧延組織が混在した状況でテンションが張られる。このとき、ΔＥに差がありすぎるとＥが小さい部分でＥが大きい部分より変形が大きくなり、Ｅの大きい部分と小さい部分の境界でシワが生じやすい。そのため、ΔＥは小さい方が好ましく、シワを効果的に抑制するためには３３ＧＰａ以下であることが必要であり、好ましくは３０ＧＰａ以下であり、より好ましくは２８ＧＰａ以下である。但し、ΔＥが小さすぎると再結晶が不十分であることが多く、屈曲特性が低下するため、ΔＥは１２ＧＰａ以上であることが必要であり、好ましくは１５ＧＰａ以上である。 In the copper clad laminate production line, due to heat treatment in the middle, the copper foil is tensioned in a state where a recrystallized structure and a rolled structure before recrystallization are mixed. At this time, if there is an excessive difference in ΔE, the deformation is larger in the portion where E is small than the portion where E is large, and wrinkles are likely to occur at the boundary between the portion where E is large and the portion where E is small. Therefore, ΔE is preferably small, and in order to effectively suppress wrinkles, it is necessary to be 33 GPa or less, preferably 30 GPa or less, more preferably 28 GPa or less. However, if ΔE is too small, recrystallization is often inadequate and the bending properties are deteriorated. Therefore, ΔE needs to be 12 GPa or more, and preferably 15 GPa or more.
（４．再結晶前のヤング率）
本発明に係る圧延銅箔は一般に圧延上がりの状態であり、圧延組織を有している。但し、脱脂後の乾燥等で再結晶しない程度の熱履歴があってもよい。本発明に係る圧延銅箔では、この時点において、２５℃における圧延方向のヤング率Ｅ１が８０〜１３０ＧＰａであることも特徴の一つである。Ｅ１が８０ＧＰａ未満であると銅箔製造過程における圧延や脱脂の際にシワが入りやすく製造製に劣るので、８０ＧＰａ以上と設定した。Ｅ１は好ましくは８５ＧＰａ以上であり、より好ましくは９５ＧＰａ以上である。一方、Ｅ１が１３０ＧＰａより大きいと再結晶後にΔＥが３３ＧＰａより大きくなりやすく、再結晶前後での物性変化に伴うシワの発生を抑制できなくなるので、１３０ＧＰａ以下に設定した。Ｅ１は好ましくは１２５ＧＰａ以下であり、より好ましくは１２０ＧＰａ以下である。
(4. Young's modulus before recrystallization)
The rolled copper foil according to the present invention is generally in a state after rolling and has a rolled structure. However, there may be a thermal history that does not cause recrystallization due to drying after degreasing. One feature of the rolled copper foil according to the present invention is that, at this point, the Young's modulus E1 in the rolling direction at 25 ° C. is 80 to 130 GPa. When E1 is less than 80 GPa, wrinkles are likely to occur during rolling and degreasing in the copper foil production process, and the production is inferior. E1 is preferably 85 GPa or more, more preferably 95 GPa or more. On the other hand, if E1 is greater than 130 GPa, ΔE tends to be greater than 33 GPa after recrystallization, and the generation of wrinkles accompanying changes in physical properties before and after recrystallization cannot be suppressed. E1 is preferably 125 GPa or less, more preferably 120 GPa or less.
（５．再結晶後のヤング率）
上述したように、銅張積層板を製造する際の加熱処理によって銅箔の組織が圧延組織から再結晶組織に変化する。本発明に係る圧延銅箔では、３５０℃で１秒間の加熱処理をした後、２５℃における圧延方向のヤング率Ｅ２が６０〜１１０ＧＰａであることも特徴の一つである。屈曲特性の観点からは、Ｅ２は小さい方が好ましく、具体的には１１０ＧＰａ以下に設定した。Ｅ２は好ましくは１００ＧＰａ以下であり、より好ましくは９０ＧＰａ以下である。但し、Ｅ２が小さすぎると、ΔＥが大きくなりやすいため、Ｅ２を６０ＧＰａ以上に設定した。Ｅ２は好ましくは６５ＧＰａ以上であり、より好ましくは７０ＧＰａ以上である。
(5. Young's modulus after recrystallization)
As described above, the structure of the copper foil changes from the rolled structure to the recrystallized structure by the heat treatment when manufacturing the copper-clad laminate. One feature of the rolled copper foil according to the present invention is that the Young's modulus E2 in the rolling direction at 25 ° C. is 60 to 110 GPa after heat treatment at 350 ° C. for 1 second. From the viewpoint of the bending characteristics, E2 is preferably small, and specifically, it is set to 110 GPa or less. E2 is preferably 100 GPa or less, more preferably 90 GPa or less. However, if E2 is too small, ΔE tends to increase, so E2 was set to 60 GPa or more. E2 is preferably 65 GPa or more, more preferably 70 GPa or more.
（６．立方体集合組織）
優れた屈曲特性を得る観点からは、再結晶後の銅箔の金属組織において立方体集合組織（｛１００｝＜００１＞方位）が発達していることが好ましい。立方体集合組織の発達の程度は、（２００）面のＸ線回折強度比Ｉ／Ｉ0（Ｉ：銅箔の２００面の回折強度、Ｉ0：ランダム方位をもつ銅粉末の（２００）面の回折強度）の大きさで表すことができ、この値が大きいほど立方体方位が発達していることを示す。Ｉ／Ｉ0は好ましくは１０以上であり、より好ましくは１５以上である。但し、Ｉ／Ｉ0は高くなりすぎると、ソフトエッチング時にディッシュダウン（皿のように窪んだ欠陥／（２００）面とその他の方位を向いた面でエッチング速度が異なること、結晶粒内と粒界でエッチング速度が異なることに起因）が発生しやすいことから、Ｉ／Ｉ0は好ましくは３０以下であり、より好ましくは２５以下である。尚、Ｉ／Ｉｏが６０以上であるとおよそ全面に（２００）面が発達した状態になるため、ディッシュダウンは発生しにくくなるが６０以上であるとΔＥが大きくなるために好ましくない。
銅粉末としては純銅標準粉末を使用し、これは３２５メッシュ（ＪＩＳ Ｚ８８０１）の純度９９．５％の銅粉末で定義される。
(6. Cube texture)
From the viewpoint of obtaining excellent bending properties, it is preferable that a cubic texture ({100} <001> orientation) is developed in the metal structure of the copper foil after recrystallization. The degree of development of the cubic texture is determined by the X-ray diffraction intensity ratio I / I 0 of the (200) plane (I: the diffraction intensity of the 200 plane of the copper foil, I 0 : the (200) plane of the copper powder having a random orientation. It can be expressed by the magnitude of (diffraction intensity), and the larger this value, the more the cube orientation is developed. I / I 0 is preferably 10 or more, more preferably 15 or more. However, if I / I 0 becomes excessively high, the etching rate is different between the dishdown (soft-etched defect / (200) plane and other orientation planes), and within the crystal grains. I / I 0 is preferably 30 or less, and more preferably 25 or less. When I / Io is 60 or more, since the (200) plane is developed on the entire surface, dishdown is difficult to occur.
A pure copper standard powder is used as the copper powder, which is defined as a copper powder having a purity of 99.5% with a 325 mesh (JIS Z8801).
（７．圧延銅箔の製造方法）
圧延銅箔の製造プロセスでは、電気銅の純銅原料を溶解して合金元素を添加した後、この溶湯を鋳造し、厚みが１００〜３００ｍｍ程度のインゴットを製造する。このインゴットに対して均質化のための焼鈍を行った後、熱間圧延して５〜２０ｍｍ程度の板にした後、冷間圧延と焼鈍を繰り返して薄くし、最後に冷間圧延（最終冷間圧延）で所定厚みの箔に仕上げる。最終冷間圧延後の銅箔には脱脂、防錆や絶縁基板との密着性向上のための粗化処理等各種表面処理を行ってもよい。
(7. Manufacturing method of rolled copper foil)
In the manufacturing process of the rolled copper foil, after melting a pure copper raw material of electrolytic copper and adding an alloy element, the molten metal is cast to manufacture an ingot having a thickness of about 100 to 300 mm. The ingot is annealed for homogenization, then hot rolled to a plate of about 5 to 20 mm, then cold rolled and annealed repeatedly to make it thinner, and finally cold rolled (final cold To a foil with a predetermined thickness. The copper foil after the final cold rolling may be subjected to various surface treatments such as degreasing, rust prevention, and roughening treatment for improving adhesion to the insulating substrate.
本発明に係る圧延銅箔を製造する上では、冷間圧延と焼鈍を繰り返すが、冷間圧延後に行うすべての焼鈍において、材料の焼鈍温度下の耐力に対し０．１〜０．５倍程度のテンションを掛けながら実施するのがよい。これは、冷間圧延後の焼鈍で形成される再結晶組織を制御することで最終圧延後の組織を制御し、Ｅ１、Ｅ２、ΔＥを制御するためである。焼鈍時にテンションをかけると再結晶に要する熱量はテンションが無いとき比べ大きくなる。また再結晶後に結晶粒が大きく成長しやすい。テンションが耐力に対して０．５倍より大きいと２次再結晶が部分的に起こり易く、その後の圧延で粗大化した結晶粒部でオレが生じ易い。０．１倍より小さいとＥ２が小さくなりやすく、ΔＥが３３ＧＰａより大きくなりやすい。また、焼鈍の条件としては、再結晶に必要な熱量を加えれば良いが例えば３５０〜８００℃で１〜２０００ｓが挙げられる。温度が低いときは焼鈍時間を長くし、高いときは焼鈍時間を短くすれば良い。更に、最終冷間圧延は銅張積層板作製時の熱によって全面が均一に再結晶するように９０〜９９．７％の加工度とするのが好ましい。ここで、加工度ｒ（％）は、ｒ＝（ｔｏ−ｔ）／ｔｏ×１００（ｔ：圧延後の厚み、ｔｏ：圧延前、焼鈍後の厚み）で定義される。また、最終冷間圧延は１パスあたりの加工度の加工度を１０〜４０％にするのが好ましい。１０％未満であるとＥ２が小さくなりやすく、ΔＥが３３ＧＰａより大きくなりやすい。４０％以上にするとＥ２が大きくなりやすく、ΔＥが１２より小さくなりやすい。ここで、１パスあたりの加工度ｒ（％）は、ｒ＝（ｔ１−ｔ２）／ｔ１×１００（ｔ１：圧延ロール入り側の厚み、ｔ２：圧延ロール出側の厚み）で定義される。 In producing the rolled copper foil according to the present invention, cold rolling and annealing are repeated, but in all the annealing performed after cold rolling, it is about 0.1 to 0.5 times the yield strength at the annealing temperature of the material. It is good to carry out while applying the tension. This is because the structure after final rolling is controlled by controlling the recrystallized structure formed by annealing after cold rolling, and E1, E2, and ΔE are controlled. When tension is applied during annealing, the amount of heat required for recrystallization is greater than when there is no tension. In addition, the crystal grains tend to grow large after recrystallization. When the tension is larger than 0.5 times the yield strength, secondary recrystallization is likely to occur partially, and burrs are likely to occur at crystal grain portions coarsened by subsequent rolling. If it is less than 0.1 times, E2 tends to be small and ΔE tends to be larger than 33 GPa. Moreover, as conditions for annealing, the amount of heat necessary for recrystallization may be added, but examples include 1 to 2000 s at 350 to 800 ° C. When the temperature is low, the annealing time may be lengthened, and when the temperature is high, the annealing time may be shortened. Further, the final cold rolling is preferably performed at a working degree of 90 to 99.7% so that the entire surface is uniformly recrystallized by heat at the time of producing the copper-clad laminate. Here, the working degree r (%) is defined by r = (to-t) / to × 100 (t: thickness after rolling, to: thickness before rolling, and thickness after annealing). Further, in the final cold rolling, it is preferable that the degree of work per pass is 10 to 40%. If it is less than 10%, E2 tends to be small, and ΔE tends to be larger than 33 GPa. If it is 40% or more, E2 tends to be large, and ΔE tends to be smaller than 12. Here, the processing degree r (%) per pass is defined by r = (t1−t2) / t1 × 100 (t1: thickness on the rolling roll entering side, t2: thickness on the rolling roll exit side).
（８．プリント配線板の製造）
本発明に係る銅箔を用いてプリント配線板（ＰＷＢ）を常法に従って製造することができる。以下に、プリント配線板の製造例を示す。
(8. Production of printed wiring boards)
A printed wiring board (PWB) can be manufactured according to a conventional method using the copper foil according to the present invention. Below, the example of manufacture of a printed wiring board is shown.
まず、銅箔と絶縁基板を貼り合わせて銅張積層板を製造する。銅箔が積層される絶縁基板はフレキシブルプリント配線板、電磁波シールド材、照明機器のリフレクタ、配線、放熱板に適用可能な特性を有するものであれば特に制限を受けないが、ポリエステルフィルムやポリイミドフィルム、液晶ポリマーフィルム等を使用する事ができる。 First, a copper-clad laminate is manufactured by bonding a copper foil and an insulating substrate. The insulating substrate on which the copper foil is laminated is not particularly limited as long as it has characteristics applicable to flexible printed wiring boards, electromagnetic shielding materials, reflectors for lighting equipment, wiring, and heat sinks, but polyester films and polyimide films A liquid crystal polymer film can be used.
フレキシブルプリント配線板（ＦＰＣ）用の場合、ポリイミドフィルム又はポリエステルフィルムと銅箔の被覆層を有する面をエポキシ系やアクリル系の接着剤を使って接着することができる（３層構造）。また、接着剤を使用しない方法（２層構造）としては、ポリイミドの前駆体であるポリイミドワニス（ポリアミド酸ワニス）を銅箔の被覆層を有する面に塗布し、加熱することでイミド化するキャスティング法や、ポリイミドフィルム上に熱可塑性のポリイミドを塗布し、その上に銅箔の被覆層を有する面を重ね合わせ、加熱加圧するラミネート法が挙げられる。キャスティング法においては、ポリイミドワニスを塗布する前に熱可塑性ポリイミド等のアンカーコート材を予め塗布しておくことも有効である。 In the case of a flexible printed wiring board (FPC), a surface having a polyimide film or polyester film and a copper foil coating layer can be bonded using an epoxy or acrylic adhesive (three-layer structure). In addition, as a method without using an adhesive (two-layer structure), a polyimide varnish (polyamic acid varnish), which is a polyimide precursor, is applied to a surface having a coating layer of copper foil, and imidized by heating. And a lamination method in which a thermoplastic polyimide is applied on a polyimide film, a surface having a copper foil coating layer is superimposed thereon, and heated and pressed. In the casting method, it is also effective to apply an anchor coating material such as thermoplastic polyimide in advance before applying the polyimide varnish.
樹脂フィルムの両側に銅箔を貼り付ける両面銅張積層板を工業的規模で製造するには、長尺の銅箔をロールトゥロールのライン上で流しながら絶縁基板への貼り合わせを行うが、貼り合わせのための加熱処理は例えば３００〜４００℃に熱せられたニップロール中を０．５〜１０ｍ／ｍｉｎ程度の速度で通板することにより行われる。本発明に係る圧延銅箔によれば、加熱による再結晶前後でのヤング率が制御されているため、シワの発生が抑制される。このため、生産性及び歩留まりの向上が期待できる。 To manufacture a double-sided copper-clad laminate with copper foil on both sides of the resin film on an industrial scale, the long copper foil is bonded to an insulating substrate while flowing on a roll-to-roll line. The heat treatment for bonding is performed, for example, by passing through a nip roll heated to 300 to 400 ° C. at a speed of about 0.5 to 10 m / min. According to the rolled copper foil which concerns on this invention, since the Young's modulus before and behind recrystallization by heating is controlled, generation | occurrence | production of a wrinkle is suppressed. For this reason, improvement in productivity and yield can be expected.
本発明に係る銅張積層板は各種のプリント配線板（ＰＷＢ）に使用可能であり、特に制限されるものではないが、例えば、導体パターンの層数の観点からは片面ＰＷＢ、両面ＰＷＢ、多層ＰＷＢ（３層以上）に適用可能であり、絶縁基板材料の種類の観点からはフレキシブルＰＷＢ（ＦＰＣ）、リジッド・フレックスＰＷＢに適用可能である。 The copper-clad laminate according to the present invention can be used for various printed wiring boards (PWB) and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, single-sided PWB, double-sided PWB, multilayer It can be applied to PWB (3 layers or more), and can be applied to flexible PWB (FPC) and rigid flex PWB from the viewpoint of the type of insulating substrate material.
銅張積層板からプリント配線板を製造する工程は当業者に周知の方法を用いればよく、例えばエッチングレジストを銅張積層板の銅箔面に導体パターンとしての必要部分だけに塗布し、エッチング液を銅箔面に噴射することで不要銅箔を除去して導体パターンを形成し、次いでエッチングレジストを剥離・除去して導体パターンを露出することができる。 The process for producing a printed wiring board from a copper clad laminate may be performed by a method well known to those skilled in the art. For example, an etching resist is applied only to a necessary portion as a conductor pattern on the copper foil surface of the copper clad laminate, and an etching solution By spraying on the copper foil surface, the unnecessary copper foil can be removed to form a conductor pattern, and then the etching resist can be peeled and removed to expose the conductor pattern.
以下、実施例及び比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例のみに制限されるものではない。 Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited only to this example.
（例１）
電気銅を真空中で溶解し、次いで、表１に示す組成の元素をそれぞれ添加し、大気中又はＡｒ雰囲気中で厚み５０ｍｍのインゴットを鋳造した。酸素含有量は大気中で鋳造したものは１５０〜３００質量ｐｐｍであり、Ａｒ雰囲気中で鋳造したものは１５質量ｐｐｍ未満であった。得られたインゴットを８００℃の温度で１０時間の加熱条件で均質化焼鈍した後、熱間圧延を施した。次いで、表面の酸化スケールを面削により除去した後に、冷間圧延と再結晶焼鈍を繰り返し、最終の冷間圧延で表１に記載の各箔厚の長尺銅箔試料を作製した。
(Example 1)
Electrolytic copper was melted in a vacuum, and then elements having the compositions shown in Table 1 were added to cast an ingot having a thickness of 50 mm in the air or in an Ar atmosphere. The oxygen content was 150-300 ppm by mass when cast in the atmosphere, and less than 15 ppm by mass when cast in an Ar atmosphere. The obtained ingot was subjected to homogenization annealing at a temperature of 800 ° C. for 10 hours, and then subjected to hot rolling. Next, after removing the oxide scale on the surface by chamfering, cold rolling and recrystallization annealing were repeated, and long copper foil samples having respective foil thicknesses shown in Table 1 were prepared by final cold rolling.
上記の製造工程において、実施例及び比較例の何れも、冷間圧延後の再結晶焼鈍はすべて６５０℃で１０秒間の加熱条件で行ったが、実施例では６５０℃での各実施例の試料の耐力に対して０．３となるテンションを圧延方向に掛けながら行い、比較例ではテンションを掛けずに行った。また、実施例では、最終圧延加工度を９５％〜９９．５％とし、最終冷間圧延のすべてのパスにおいて一パスあたりの加工度を１５〜３５％内に入るよう制御したのに対し、比較例ではすべて最終圧延加工度を９２％〜９９．５％とし、最終冷間圧延のすべてのパスにおいて、比較例２では一パスあたりの加工度を５〜１５％、比較例３では一パスあたりの加工度を１５〜３５％とし、比較例１では３０〜５０％に入るように制御した。また、最終冷間圧延時の圧延油の温度は特に制御しなかった。 In the above production process, in all of the examples and comparative examples, all recrystallization annealing after cold rolling was performed under heating conditions at 650 ° C. for 10 seconds. In the examples, the samples of each example at 650 ° C. This was performed while applying a tension of 0.3 to the proof stress in the rolling direction, and in the comparative example, the tension was not applied. Further, in the examples, the final rolling work degree was set to 95% to 99.5%, and the working degree per pass was controlled to fall within 15 to 35% in all passes of the final cold rolling, In all of the comparative examples, the final rolling degree is 92% to 99.5%. In all the passes of the final cold rolling, the comparative example 2 has a working degree per pass of 5 to 15%, and the comparative example 3 has one pass. The degree of processing was set to 15 to 35%, and in Comparative Example 1, it was controlled to fall within 30 to 50%. Further, the temperature of the rolling oil during the final cold rolling was not particularly controlled.
得られた銅箔試料に対して、以下の特性を評価した。 The following characteristics were evaluated with respect to the obtained copper foil sample.
（ヤング率の測定）
圧延上がり銅箔試料の圧延方向におけるヤング率（Ｅ１）を、２５℃の温度条件下とした他は、振動法（ＪＩＳ Ｚ２２８０）に準拠して測定した。また、銅箔試料に対し３５０℃で１秒間の加熱プレス（プレス圧：３０ＭＰａ）を施し、熱処理後の銅箔の圧延方向におけるヤング率（Ｅ２）を２５℃の温度条件下で同様の方法で測定した。測定装置には日本テクノプラス株式会社製の片持ち式薄板ヤング率測定装置、ＴＥ−ＲＴを用いた。試料は幅３．２ｍｍ、長さ１５ｍｍの短冊形状とし、振動長さを１０ｍｍとした。ヤング率は１０回測定して平均値を測定値とした。
(Measurement of Young's modulus)
The Young's modulus (E1) in the rolling direction of the rolled copper foil sample was measured according to the vibration method (JIS Z2280) except that the temperature condition was 25 ° C. Also, the copper foil sample was subjected to a heat press (press pressure: 30 MPa) at 350 ° C. for 1 second, and the Young's modulus (E2) in the rolling direction of the copper foil after the heat treatment was measured in the same manner under a temperature condition of 25 ° C. It was measured. As a measuring device, a cantilever type thin plate Young's modulus measuring device, TE-RT manufactured by Nippon Techno Plus Co., Ltd. was used. The sample had a strip shape with a width of 3.2 mm and a length of 15 mm, and the vibration length was 10 mm. The Young's modulus was measured 10 times and the average value was taken as the measured value.
（Ｉ／Ｉ0の測定）
３５０℃で１秒間の加熱プレス（プレス圧：３０ＭＰａ）を施した後の銅箔試料について、圧延面のＸ線回折（リガク社製型式ＲＩＮＴ−２５００）で（２００）面の回折強度の積分値（Ｉ）を求めた。この値を予め測定しておいた微粉末銅（３２５ｍｅｓｈ）の（２００）回折強度の積分値（Ｉ0）で割り、Ｉ／Ｉ0値を計算した。Ｘ線回折はＣｏ管球を用いて行い、（２００）面の回折強度の積分値は、２θ＝５７〜６３°（θは回折角度）の範囲で測定した。
(Measurement of I / I 0 )
The integrated value of the diffraction intensity of the (200) plane in the X-ray diffraction of the rolled surface (model RINT-2500, manufactured by Rigaku Corporation) for the copper foil sample after being heated and pressed at 350 ° C. for 1 second (press pressure: 30 MPa). (I) was determined. This value was divided by the integral value (I 0 ) of (200) diffraction intensity of finely powdered copper (325 mesh), which had been measured in advance, to calculate an I / I 0 value. X-ray diffraction was performed using a Co tube, and the integrated value of the diffraction intensity of the (200) plane was measured in the range of 2θ = 57 to 63 ° (θ is the diffraction angle).
（シワの抑制）
圧延上がり銅箔試料と厚み１２μｍのポリイミドフィルム（カプトンＥＮ）に市販の熱可塑性ポリイミド接着剤を塗工、乾燥して作製した厚み１５μｍの接着剤付きポリイミドフィルムを積層して３５０℃に加熱されたニップロール中を通板するラミネート試験にて熱圧着して銅張積層板を製造した。銅箔巻き出しのテンションを３０ＭＰａ、通板速度を０．５〜１０ｍ／ｍｉｎで変化させ、すべての速度で熱圧着時にシワが入ったものをシワの抑制×、０．５〜３ｍ／ｍｉｎでシワが入らなかったものをシワの抑制○、０．５〜１ｍ／ｍｉｎでシワが入らなかったものをシワの抑制△、すべての速度でシワが入らなかったものをシワの抑制◎とした。
(Wrinkle suppression)
Rolled copper foil sample and 12 μm thick polyimide film (Kapton EN) were coated with a commercially available thermoplastic polyimide adhesive and dried, and a 15 μm thick polyimide film with adhesive was laminated and heated to 350 ° C. A copper-clad laminate was manufactured by thermocompression bonding in a laminating test in which the sheet was passed through a nip roll. The tension of copper foil unwinding was changed to 30 MPa, the sheet passing speed was changed from 0.5 to 10 m / min, and wrinkles were suppressed at the time of thermocompression bonding at all speeds, with wrinkle suppression x, 0.5 to 3 m / min. Wrinkles were suppressed when the wrinkles did not enter, and wrinkles were suppressed when the wrinkles did not enter at 0.5 to 1 m / min, and wrinkles were suppressed when no wrinkles occurred at all speeds.
（ソフトエッチング性）
ソフトエッチングを行った後、外観を光学顕微鏡により検査した。ディッシュダウンとよばれる面積率の少ない方の面は多い方の面に囲まれて存在するが、その内、短径が５０μｍを超える箇所の個数を数えた。ソフトエッチング剤として、アデカテックＣＬ−８（株式会社アデカ製）を用いて常温で２分間エッチングを行い、エッチング後の１ｍｍ四方の観察範囲の表面を光学顕微鏡で撮影した画像を明暗二値化し、明暗の割合を算出した。積率の少ない方の面は多い方の面に囲まれて存在するが、その内短径が５０μｍを超える箇所の個数を数えた。当該箇所が７以下である場合をエッチング性最良好（◎）、１０以下である場合をエッチング性良好（○）とし、１０個より多かった場合をエッチング性劣（×）とした。
(Soft etching)
After soft etching, the appearance was inspected with an optical microscope. Although the surface with a smaller area ratio called dish down is surrounded by the surface with the larger area, the number of locations where the minor axis exceeds 50 μm was counted. Etching is performed for 2 minutes at room temperature using Adeka Tech CL-8 (manufactured by Adeka Co., Ltd.) as a soft etchant, and an image obtained by photographing the surface of the observation range of 1 mm square after etching with an optical microscope is converted into light and dark. The percentage of was calculated. Although the surface with the smaller volume fraction is surrounded by the surface with the larger volume, the number of locations where the inner minor axis exceeds 50 μm was counted. When the location was 7 or less, the etching property was the best (◎), and when it was 10 or less, the etching property was good (◯), and when it was more than 10, the etching property was poor (x).
（屈曲疲労特性）
厚み２５μｍのポリイミドフィルム（商品名：カプトンＥＮ）に市販の熱可塑性ＰＩ接着剤を２μｍ塗工、乾燥して形成した２７μｍ厚の樹脂層を銅箔に積層させて真空熱プレスによって銅張積層体を作製した。図１に示す屈曲試験装置により、屈曲疲労寿命の測定を行った。この装置は、発振駆動体４に振動伝達部材３を結合した構造になっており、被試験体１は、矢印で示したねじ２の部分と振動部３の先端部の計４点で装置に固定される。振動部３が上下に駆動すると、被試験体１の中間部は、所定の曲率半径ｒでヘアピン状に屈曲される。本試験では、以下の条件下で屈曲を繰り返した時の破断までの回数を求めた。
試験条件は次の通りである：試験片幅：１２．７ｍｍ、試験片長さ：２００ｍｍ、試験片採取方向：試験片の長さ方向が圧延方向と平行になるように採取、曲率半径ｒ：２．５ｍｍ、振動ストローク：２５ｍｍ、振動速度：１５００回／分。
屈曲疲労寿命が６０万回以上の場合に◎、５０万回以上の場合に○、５０万回未満の場合×とした。
(Bending fatigue properties)
A 27 μm thick resin layer formed by applying 2 μm of a commercially available thermoplastic PI adhesive to a polyimide film (trade name: Kapton EN) having a thickness of 25 μm and drying it is laminated on a copper foil, and a copper-clad laminate by vacuum hot pressing. Was made. The bending fatigue life was measured by the bending test apparatus shown in FIG. This apparatus has a structure in which a vibration transmitting member 3 is coupled to an oscillation driver 4, and the device under test 1 is connected to the apparatus at a total of four points: a screw 2 portion indicated by an arrow and a tip portion of the vibration portion 3. Fixed. When the vibration part 3 is driven up and down, the intermediate part of the DUT 1 is bent into a hairpin shape with a predetermined radius of curvature r. In this test, the number of times until breakage when bending was repeated under the following conditions was determined.
The test conditions are as follows: Specimen width: 12.7 mm, Specimen length: 200 mm, Specimen sampling direction: Sampled so that the length direction of the specimen is parallel to the rolling direction, radius of curvature r: 2 0.5 mm, vibration stroke: 25 mm, vibration speed: 1500 times / minute.
When the bending fatigue life is 600,000 times or more, ◎, when it is 500,000 times or more, ○, when it is less than 500,000 times, ×.
（最終圧延後の外観）
最終圧延、脱脂後に銅箔表面を市販のCCDラインセンサーにより６００ｍ2観察し、他の場所と色調が異なるスジが全くないものを◎、他の場所と色調が異なるスジが１箇所以上発生○、他の場所と色調が異なるスジが１箇所以上発生し、スジ状の部分に１箇所以上ピンホールが出来ていたものを△とした。
(Appearance after final rolling)
After final rolling and degreasing, the surface of the copper foil is observed with a commercially available CCD line sensor at 600 m 2 , and there is no streak that has a different color tone from other places. A case where one or more streaks having a color tone different from that of other places occurred and one or more pinholes were formed in the streaky portion was designated as Δ.
結果を表１に示す。実施例１〜２４では、Ｅ１、Ｅ２及びΔＥが共に適切に制御されていたことから、熱処理前後でシワの発生が抑制されている。また、実施例１〜２４では、屈曲性に優れており、圧延、脱脂時のシワも抑制されていた。更に、実施例１〜２１、２３、２４では、Ｉ／Ｉ0も適切に制御されており、ソフトエッチング性にも優れていた。
一方で、比較例１は最終冷間圧延の一パスあたりの加工度が大きかったため、ΔＥが小さすぎたことから屈曲性が実施例に比べて劣っていた。比較例２は最終圧延の一パスあたりの加工度が低すぎたためにΔＥが大きすぎたことから熱処理に伴うシワの発生が見られた。比較例３は中間焼鈍でのテンションをかけなかったためにΔＥが大きすぎたことから熱処理に伴うシワの発生が見られた。
The results are shown in Table 1. In Examples 1 to 24, since E1, E2, and ΔE were all appropriately controlled, generation of wrinkles was suppressed before and after the heat treatment. Moreover, in Examples 1-24, it was excellent in the flexibility and the wrinkle at the time of rolling and degreasing was also suppressed. Further, in Examples 1 to 21, 23, and 24, I / I 0 was also appropriately controlled, and the soft etching property was excellent.
On the other hand, in Comparative Example 1, since the degree of processing per pass of the final cold rolling was large, ΔE was too small, so that the flexibility was inferior to that of the example. In Comparative Example 2, since the degree of processing per one pass of final rolling was too low, ΔE was too large, so that wrinkles due to heat treatment were observed. In Comparative Example 3, since ΔE was too large because no tension was applied in the intermediate annealing, generation of wrinkles due to heat treatment was observed.
（例２：特開２０１２−００１７８６号公報に記載された銅箔に相当する比較例）
電気銅を真空中で溶解し、次いで、表２に示す組成の元素をそれぞれ添加し、大気中でインゴットを鋳造した。酸素含有量は大気中で鋳造したものは１５０〜３００質量ｐｐｍであった。得られたインゴットを８５０℃の温度で３時間の加熱条件で加熱した後、熱間圧延を施した。次いで、表面の酸化スケールを面削により除去した後に、冷間圧延と再結晶焼鈍を繰り返し、最終の冷間圧延で厚み１２μｍの長尺銅箔試料を作製した。
上記の製造工程において、冷間圧延後の再結晶焼鈍はすべて６５０℃で１０秒間の加熱条件でテンションを掛けずに行った。また、最終圧延加工度を９５％〜９９．９％とした。また、最終冷間圧延時の圧延油の温度を３０〜４０℃の範囲に調整した。
(Example 2: Comparative example corresponding to the copper foil described in JP2012-001786A)
The electrolytic copper was dissolved in a vacuum, and then elements having the compositions shown in Table 2 were added to cast the ingot in the atmosphere. What was cast in air | atmosphere was 150-300 mass ppm for oxygen content. The obtained ingot was heated at a temperature of 850 ° C. for 3 hours and then hot-rolled. Next, after removing the oxide scale on the surface by chamfering, cold rolling and recrystallization annealing were repeated, and a long copper foil sample having a thickness of 12 μm was produced by the final cold rolling.
In the above manufacturing process, all recrystallization annealing after cold rolling was performed at 650 ° C. for 10 seconds without applying tension. Further, the final rolling work degree was set to 95% to 99.9%. Moreover, the temperature of the rolling oil at the time of final cold rolling was adjusted to the range of 30-40 degreeC.
得られた銅箔試料に対して、例１と同様に特性評価を行った。また、参考用に３６０℃で６分間加熱プレス（プレス圧：３０ＭＰａ）した後のヤング率（Ｅ３）を２５℃の温度条件下で例１と同様の方法で測定した。結果を表２に示す。比較例４、６は再結晶焼鈍でテンションをかけなかったこと、最終圧延での１パスあたりの加工度を制御しなかったためにΔＥが大きすぎたことから熱処理に伴うシワの発生が見られた。比較例５は最終圧延の加工度が大きすぎたためにΔＥが小さすぎたことから屈曲性が実施例に比べて劣っていた。 The obtained copper foil sample was evaluated for characteristics in the same manner as in Example 1. Further, for reference, Young's modulus (E3) after heating and pressing at 360 ° C. for 6 minutes (press pressure: 30 MPa) was measured in the same manner as in Example 1 under a temperature condition of 25 ° C. The results are shown in Table 2. In Comparative Examples 4 and 6, wrinkles due to heat treatment were observed because ΔE was too large because no tension was applied by recrystallization annealing and the degree of processing per pass in final rolling was not controlled. . In Comparative Example 5, since the degree of work of the final rolling was too large, ΔE was too small, so that the flexibility was inferior to that of the example.
（例３：特開２００９−１５８３８２号公報に記載された銅箔に相当する比較例）
電気銅を真空中で溶解し、Ａｒ雰囲気中でインゴットを鋳造した。得られたインゴットを加熱した後、熱間圧延を施した。次いで、表面の酸化スケールを面削により除去した後に、冷間圧延と再結晶焼鈍を繰り返し、最終の冷間圧延で厚み１８μｍの長尺銅箔試料を作製した。但し、再結晶焼鈍においてはテンションをかけず、最終圧延での１パスあたりの加工度も制御しなかった。
(Example 3: Comparative example corresponding to the copper foil described in JP2009-158382A)
Electro-copper was melted in a vacuum and an ingot was cast in an Ar atmosphere. The obtained ingot was heated and then hot-rolled. Next, after removing the oxide scale on the surface by chamfering, cold rolling and recrystallization annealing were repeated, and a long copper foil sample having a thickness of 18 μm was produced by the final cold rolling. However, no tension was applied in the recrystallization annealing, and the degree of processing per pass in the final rolling was not controlled.
得られた銅箔試料に対して、例１と同様に特性評価を行った。また、参考用に３００℃で５分間加熱プレス（プレス圧：３０ＭＰａ）する前後に引張試験を行い、応力−歪み曲線における原点付近での傾き（加熱プレス前をＥ４、加熱プレス後をＥ５）を２５℃の温度条件下で測定した。結果を表３に示す。比較例７、８は再結晶焼鈍でテンションをかけなかったこと、最終圧延での１パスあたりの加工度を制御しなかったためにΔＥが大きすぎたことから熱処理に伴うシワの発生が見られた。 The obtained copper foil sample was evaluated for characteristics in the same manner as in Example 1. For reference, a tensile test was performed before and after heating press at 300 ° C. for 5 minutes (press pressure: 30 MPa), and the slopes near the origin in the stress-strain curve (E4 before heating press, E5 after heating press). Measurement was performed under a temperature condition of 25 ° C. The results are shown in Table 3. In Comparative Examples 7 and 8, since no tension was applied by recrystallization annealing, and the degree of processing per pass in the final rolling was not controlled, ΔE was too large, so that generation of wrinkles due to heat treatment was observed. .
１．被試験体
２．ねじ
３．振動伝達部材
４．発振駆動体
1. 1. Device under test Screw 3. 3. Vibration transmission member Oscillation driver
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| JP2017183459A (en) * | 2016-03-30 | 2017-10-05 | Ｊｘ金属株式会社 | Copper foil, copper clad laminate sheet, flexible printed circuit board and electronic apparatus |
| WO2017095346A3 (en) * | 2015-11-30 | 2017-10-12 | Dokuz Eylul Universitesi Rektorlugu | Method of producing antibacterial copper sheets having a shape being suitable to coat the surface of objects and their uses |
| JP2023024926A (en) * | 2021-08-09 | 2023-02-21 | ▲き▼邦科技股▲分▼有限公司 | Flexible circuit board and heat sink thereof |
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| JP2012001786A (en) * | 2010-06-18 | 2012-01-05 | Jx Nippon Mining & Metals Corp | Flexible copper-clad laminate, and method of manufacturing the same |
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| JP2012001786A (en) * | 2010-06-18 | 2012-01-05 | Jx Nippon Mining & Metals Corp | Flexible copper-clad laminate, and method of manufacturing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017043789A (en) * | 2015-08-24 | 2017-03-02 | Ｄｏｗａメタルテック株式会社 | Cu-Ni-Co-Si-BASED HIGH STRENGTH COPPER ALLOY THIN SHEET MATERIAL AND MANUFACTURING METHOD THEREFOR, AND CONDUCTIVE SPRING MEMBER |
| WO2017095346A3 (en) * | 2015-11-30 | 2017-10-12 | Dokuz Eylul Universitesi Rektorlugu | Method of producing antibacterial copper sheets having a shape being suitable to coat the surface of objects and their uses |
| JP2017183459A (en) * | 2016-03-30 | 2017-10-05 | Ｊｘ金属株式会社 | Copper foil, copper clad laminate sheet, flexible printed circuit board and electronic apparatus |
| JP2023024926A (en) * | 2021-08-09 | 2023-02-21 | ▲き▼邦科技股▲分▼有限公司 | Flexible circuit board and heat sink thereof |
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| JP5753115B2 (en) | 2015-07-22 |
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