TWI730280B - Copper foil for flexible printed circuit boards, copper-clad laminates using the same, flexible printed circuit boards and electronic devices - Google Patents
Copper foil for flexible printed circuit boards, copper-clad laminates using the same, flexible printed circuit boards and electronic devices Download PDFInfo
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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Abstract
本發明提供一種蝕刻性優異之可撓性印刷基板用銅箔、使用其之覆銅積層體、可撓性印刷基板及電子機器。 The present invention provides a copper foil for a flexible printed circuit board with excellent etching properties, a copper-clad laminate, a flexible printed circuit board, and an electronic device using the copper foil.
本發明之可撓性印刷基板用銅箔係由99.0質量%以上之Cu、及剩餘部分之不可避免之雜質所構成之銅箔，且平均結晶粒徑為0.5~4.0μm，銅箔表面之由X射線繞射強度I(220)/I0(220)所表示之集合度為1.3以上且未達7.0，導電率為80%以上。 The copper foil for a flexible printed circuit board of the present invention is a copper foil composed of 99.0% by mass or more of Cu and the remainder of inevitable impurities, and the average crystal grain size is 0.5 to 4.0 μm. The surface of the copper foil The X-ray diffraction intensity I (220)/I 0 (220) indicates the aggregation degree is 1.3 or more and less than 7.0, and the conductivity is 80% or more.
Description
本發明係關於一種可較佳地用於可撓性印刷基板等配線構件之銅箔、使用其之覆銅積層體、可撓性配線板及電子機器。 The present invention relates to a copper foil that can be preferably used for wiring members such as a flexible printed circuit board, a copper-clad laminate using the same, a flexible wiring board, and an electronic device.
可撓性印刷基板(可撓性配線板，以下稱為「FPC」)由於具有可撓性，故被廣泛用於電子電路之彎折部或可動部。例如，將FPC用於HDD或DVD及CD-ROM等碟片相關機器之可動部、摺疊式行動電話機之彎折部等。 Flexible printed circuit boards (flexible wiring boards, hereinafter referred to as "FPC") are widely used for bending or movable parts of electronic circuits due to their flexibility. For example, FPC is used in the movable part of HDD, DVD and CD-ROM and other disc-related equipment, and the folding part of foldable mobile phone.
FPC係藉由將積層銅箔與樹脂而成之Copper Clad Laminate(覆銅積層體，以下稱為CCL)蝕刻而形成配線，且其上經被稱為覆蓋層(cover lay)之樹脂層被覆而成者。於積層覆蓋層之前階段中，作為用以提高銅箔與覆蓋層之密接性之表面改質步驟之一環，進行銅箔表面之蝕刻。又，亦存在為了減少銅箔之厚度提高彎曲性，而進行減厚蝕刻之情形。 FPC is formed by etching Copper Clad Laminate (CCL), which is a laminate of copper foil and resin, to form wiring, and it is covered with a resin layer called a cover lay. Winner. In the stage before the build-up of the cover layer, as one of the surface modification steps to improve the adhesion between the copper foil and the cover layer, the surface of the copper foil is etched. In addition, in order to reduce the thickness of the copper foil and improve the flexibility, thickness reduction etching may be performed.
再者，隨著電子機器之小型、薄型、高性能化，要求FPC之電路寬度、間隔寬度之微細化(例如，20~30μm左右)。若FPC之電路微細化，則存在以下問題，即，於藉由蝕刻形成電路時，蝕刻因子(etching factor)或電路直線性容易劣化(專利文獻1，2)。
Furthermore, as electronic devices become smaller, thinner, and higher-performance, the circuit width and interval width of the FPC are required to be miniaturized (for example, about 20 to 30 μm). If the circuit of the FPC is miniaturized, there is a problem that when the circuit is formed by etching, the etching factor or the linearity of the circuit is easily deteriorated (
[先前技術文獻] [Prior Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2017-141501號公報 [Patent Document 1] JP 2017-141501 A
[專利文獻2]日本特開2017-179390號公報 [Patent Document 2] JP 2017-179390 A
然而，於習知之技術中，作為改善蝕刻性之方案，進行了平均結晶粒徑等之最佳化，但微細電路之形成中之蝕刻性仍有改善之餘地。 However, in the conventional technique, as a solution to improve the etching properties, optimization of the average crystal grain size, etc., has been carried out, but there is still room for improvement in the etching properties in the formation of fine circuits.
本發明係為了解決上述課題而成者，其目的在於提供一種蝕刻性優異之可撓性印刷基板用銅箔、使用其之覆銅積層體、可撓性印刷基板及電子機器。 The present invention was made in order to solve the above-mentioned problems, and its object is to provide a copper foil for a flexible printed circuit board with excellent etching properties, a copper-clad laminate using the same, a flexible printed circuit board, and an electronic device.
本發明者等人進行了各種研究，其結果發現〈220〉方位之蝕刻速度較大。尤其於利用氯化銅蝕刻劑之蝕刻中，不存在由方位所致之蝕刻速度之差。因此，藉由增多〈220〉方位之晶粒，而成功地進一步提高了蝕刻性(特別是軟蝕刻性及蝕刻因子)。 The inventors of the present invention conducted various studies, and as a result, found that the etching speed in the <220> orientation is relatively high. Especially in the etching using copper chloride etchant, there is no difference in etching speed due to orientation. Therefore, by increasing the crystal grains in the <220> orientation, the etching properties (especially the soft etching properties and etching factors) have been further improved successfully.
即，本發明之可撓性印刷基板用銅箔係由99.0質量%以上之Cu、及剩餘部分之不可避免之雜質所構成之壓延銅箔，且平均結晶粒徑為0.5~4.0μm，銅箔表面之由X射線繞射強度I(220)/I0(220)所表示之集合度為1.3以上且未達7.0，導電率為80%以上。 That is, the copper foil for a flexible printed circuit board of the present invention is a rolled copper foil composed of 99.0% by mass or more of Cu and the remainder of inevitable impurities, and the average crystal grain size is 0.5 to 4.0 μm. The copper foil The aggregation degree represented by the X-ray diffraction intensity I (220)/I 0 (220) of the surface is 1.3 or more and less than 7.0, and the conductivity is 80% or more.
本發明之可撓性印刷基板用銅箔較佳為由JIS-H3100(C1100)標準之精銅或JIS-H3100(C1020)之無氧銅所構成。 The copper foil for a flexible printed circuit board of the present invention is preferably composed of JIS-H3100 (C1100) standard refined copper or JIS-H3100 (C1020) oxygen-free copper.
本發明之可撓性印刷基板用銅箔較佳為進而含有合計為0.7質量%以下之選自由P、Ag、Si、Ge、Al、Ga、Zn、Sn及Sb所組成之群中之至少1種或2種以上作為添加元素而成。 The copper foil for a flexible printed circuit board of the present invention preferably further contains at least 1 selected from the group consisting of P, Ag, Si, Ge, Al, Ga, Zn, Sn, and Sb in a total of 0.7% by mass or less One or two or more types are used as additional elements.
於本發明之可撓性印刷基板用銅箔中，較佳為於300℃×30min退火(其中，升溫速度為100℃/min~300℃/min)後，上述平均結晶粒徑為0.5~4.0μm，上述集合度為1.3以上且未達7.0，上述導電率為80%以上。 In the copper foil for flexible printed circuit boards of the present invention, it is preferable to anneal at 300℃×30min (wherein, the heating rate is 100℃/min~300℃/min), and the average crystal grain size is 0.5~4.0 μm, the aggregation degree is 1.3 or more and less than 7.0, and the electrical conductivity is 80% or more.
本發明之覆銅積層體係積層上述可撓性印刷基板用銅箔與樹脂層而成。 The copper clad laminate system of the present invention is formed by laminating the above-mentioned copper foil for a flexible printed circuit board and a resin layer.
本發明之可撓性印刷基板係於上述覆銅積層體中之上述銅箔上形成電路而成。 The flexible printed circuit board of the present invention is formed by forming a circuit on the copper foil in the copper-clad laminate.
本發明之電子機器係使用上述可撓性印刷基板而成。 The electronic device of the present invention is formed by using the above-mentioned flexible printed circuit board.
根據本發明，可獲得蝕刻性(特別是軟蝕刻性及蝕刻因子)優異之可撓性印刷基板用銅箔。 According to the present invention, a flexible printed circuit board copper foil having excellent etching properties (especially soft etching properties and etching factors) can be obtained.
圖1係表示蝕刻因子EF之測定方法之圖。 Figure 1 is a diagram showing the method of measuring the etching factor EF.
圖2係表示蝕刻因子EF之測定方法之另一圖。 Fig. 2 is another diagram showing the method of measuring the etching factor EF.
以下，就本發明之銅箔之實施形態加以說明。再者，於本發明中，%除非特別說明，否則表示質量%。 Hereinafter, the embodiment of the copper foil of the present invention will be described. Furthermore, in the present invention,% means mass% unless otherwise specified.
首先，就蝕刻性中之軟蝕刻性及蝕刻因子EF加以說明。 First, the soft etching property and the etching factor EF in the etching property will be explained.
軟蝕刻性係表示由銅箔表面與抗蝕劑之密接性所引起之利用蝕刻而得之電路之精度之指標，抗蝕劑之密接性越佳而抗蝕劑越追隨銅箔表面，則越抑制蝕刻液侵入兩者間而電路之一部分缺少之缺陷，於銅箔整個面可獲得均勻之電路 圖案，良率提高。 Soft etchability is an indicator of the accuracy of the circuit obtained by etching caused by the adhesion between the surface of the copper foil and the resist. The better the adhesion of the resist and the more the resist follows the surface of the copper foil, the more Suppress the defect that the etching solution penetrates between the two and a part of the circuit is missing, and a uniform circuit can be obtained on the entire surface of the copper foil Pattern, the yield rate is improved.
蝕刻因子EF係藉由蝕刻所形成之電路之剖面形狀之指標，EF越高，則藉由蝕刻所形成之電路之剖面變得越陡峭，因此，於使電路微細化時，電路圖案之精度提高。 The etching factor EF is an index of the cross-sectional shape of the circuit formed by etching. The higher the EF, the steeper the cross-section of the circuit formed by etching. Therefore, when the circuit is made finer, the accuracy of the circuit pattern improves .
於即便軟蝕刻性良好，但蝕刻因子EF較差之情形時，雖於銅箔整個面可獲得均勻之電路圖案而良率提高，但於使電路微細化時，電路圖案之精度降低。 Even if the soft etching performance is good, but the etching factor EF is poor, although a uniform circuit pattern can be obtained on the entire surface of the copper foil and the yield is improved, when the circuit is made finer, the accuracy of the circuit pattern is reduced.
相反地，於即便蝕刻因子EF良好，但軟蝕刻性較差之情形時，雖於使電路微細化時，電路圖案之精度提高，但(由於蝕刻液易侵入銅箔表面與抗蝕劑之間)而產生電路之一部分缺少之缺陷，於銅箔整個面無法獲得均勻之電路圖案而良率降低。 On the contrary, even if the etching factor EF is good, but the soft etching performance is poor, the accuracy of the circuit pattern is improved when the circuit is made finer (because the etching solution easily penetrates between the surface of the copper foil and the resist) The defect that a part of the circuit is missing occurs, and a uniform circuit pattern cannot be obtained on the entire surface of the copper foil, and the yield rate is reduced.
<組成> <composition>
本發明之銅箔係由99.0質量%以上之Cu、及剩餘部分之不可避免之雜質所構成。 The copper foil of the present invention is composed of 99.0% by mass or more of Cu and the remainder of unavoidable impurities.
於本發明之實施例中，藉由使銅箔之最終冷軋前之結晶粒徑微細化，冷軋中銅箔之差排之累積得到促進，於再結晶時再結晶晶粒變得微細。又，若於冷軋之最終道次中極端地提高應變速度，則於再結晶時再結晶晶粒配向於特定之方位，即{200}面集合度受到抑制，且可提高{220}面集合度，蝕刻性提高。 In the embodiment of the present invention, by making the crystal grain size before the final cold rolling of the copper foil finer, the accumulation of the difference in the copper foil during cold rolling is promoted, and the recrystallized grains become fine during recrystallization. In addition, if the strain rate is extremely increased in the final pass of cold rolling, the recrystallized grains will align in a specific direction during recrystallization, that is, the {200} plane aggregation degree is suppressed, and the {220} plane aggregation can be increased The degree of etching is improved.
又，為了使銅箔之再結晶後之晶粒微細化，較佳為於反覆進行退火與壓延之整個步驟之中，將於最終退火後進行之最終冷軋前之結晶粒徑設為5μm以上且20μm以下。 In addition, in order to refine the crystal grains of the copper foil after recrystallization, it is preferable to set the crystal grain size to 5 μm or more before the final cold rolling after the final annealing during the entire steps of annealing and rolling. And below 20μm.
具體而言，若調整最終退火之溫度、及最終退火前之冷軋之加工度，則可控制上述粒徑。最終退火之溫度雖根據銅箔之製造條件而變化，但並無限定，例如只要設為300~400℃即可。又，最終退火前之冷軋之加工度亦無限定，例 如只要將加工度η設為1.6~3.0即可。 Specifically, if the temperature of the final annealing and the processing degree of cold rolling before the final annealing are adjusted, the above-mentioned grain size can be controlled. Although the temperature of the final annealing changes according to the manufacturing conditions of the copper foil, it is not limited, for example, as long as it is set to 300-400 degreeC. In addition, the degree of cold rolling before final annealing is not limited. As long as the processing degree η is set to 1.6~3.0.
加工度η係將即將進行最終退火前之冷軋之材料之厚度設為A0，將剛進行完最終退火前之冷軋之材料之厚度設為A1，而由η=ln(A0/A1)所表示。 The processing degree η is the thickness of the cold-rolled material immediately before the final annealing is set to A0, and the thickness of the cold-rolled material just before the final annealing is set to A1, and is determined by η=ln(A0/A1) Said.
於最終冷軋前之結晶粒徑超過20μm之情形時，加工時之差排之相互交截變小，應變之累積變少，因此有於再結晶後應變未釋放而晶粒之微細化變得不充分之傾向。於最終冷軋前之結晶粒徑小於5μm之情形時，加工時之差排之相互交截於銅箔之大致整個區域發生，無法發生更多之相互交截，於銅箔之再結晶時再結晶晶粒微細化之效果飽和。因此，將最終冷軋前之結晶粒徑之下限設為5μm。 When the crystal grain size before the final cold rolling exceeds 20μm, the cross-cutting of the difference row during processing becomes smaller and the accumulation of strain becomes less. Therefore, the strain is not released after recrystallization and the grain size becomes finer. Tendency to be insufficient. When the crystal grain size before the final cold rolling is less than 5μm, the cross-cutting of the differences during processing occurs in approximately the entire area of the copper foil, and no more cross-cutting occurs. It will be recrystallized when the copper foil is recrystallized. The effect of crystal grain refinement is saturated. Therefore, the lower limit of the crystal grain size before the final cold rolling is set to 5 μm.
又，若相對於上述組成而含有合計為0.7質量%以下之選自由P、Ag、Si、Ge、Al、Ga、Zn、Sn及Sb所組成之群中之至少1種或2種以上作為添加元素，則可使再結晶晶粒微細化。 Also, if at least one or two or more selected from the group consisting of P, Ag, Si, Ge, Al, Ga, Zn, Sn, and Sb are contained in a total of 0.7% by mass or less relative to the above composition as an additive Elements can make the recrystallized grains finer.
上述添加元素於冷軋時使差排之相互交截之頻率增加，故再結晶晶粒可微細化。 The above-mentioned additive elements increase the frequency of the cross-cutting of the difference row during cold rolling, so that the recrystallized grains can be made finer.
若含有合計超過0.7質量%之上述添加元素，則導電率降低，存在不適合作為可撓性基板用銅箔之情形，因此將0.7質量%設為上限。上述添加元素之含量之下限並無特別限制，然而例如關於各元素，工業上難以控制為小於0.0005質量%，故將各元素之含量之下限設為0.0005質量%即可。 If the above-mentioned additive elements are contained in a total amount exceeding 0.7% by mass, the electrical conductivity may decrease and may be unsuitable as a copper foil for flexible substrates. Therefore, 0.7% by mass is set as the upper limit. The lower limit of the content of the above-mentioned additional elements is not particularly limited. However, for example, regarding each element, it is industrially difficult to control it to less than 0.0005 mass%, so the lower limit of the content of each element may be set to 0.0005 mass%.
亦可將本發明之銅箔設為由JIS-H3100(C1100)標準之精銅(TPC)或JIS-H3100(C1020)之無氧銅(OFC)所構成之組成。 The copper foil of the present invention can also be made of JIS-H3100 (C1100) standard refined copper (TPC) or JIS-H3100 (C1020) oxygen-free copper (OFC).
又，對於上述TPC或OFC，亦可設為含有P而成之組成。 In addition, the above-mentioned TPC or OFC may also be a composition containing P.
<平均結晶粒徑> <Average crystal grain size>
銅箔之平均結晶粒徑為0.5~4.0μm。若平均結晶粒徑未達0.5μm，則強度變得過高，彎曲剛性變大，彈回量(spring back)變大，不適合可撓性印刷基板 用途。若平均結晶粒徑超過4.0μm，則軟蝕刻性劣化。 The average crystal grain size of copper foil is 0.5~4.0μm. If the average crystal grain size is less than 0.5μm, the strength will be too high, the bending rigidity will increase, and the spring back will increase, making it unsuitable for flexible printed circuit boards. use. If the average crystal grain size exceeds 4.0 μm, the soft etching property deteriorates.
平均結晶粒徑之測定為了避免誤差，對箔表面以100μm×100μm之視域觀察3視域以上而進行。箔表面之觀察可使用SIM(Scanning Ion Microscope)或SEM(Scanning Electron Microscope)，基於JIS-H0501求出平均結晶粒徑。然而，雙晶係看作不同之晶粒進行測定。 In order to avoid errors, the average crystal grain size was measured by observing more than 3 fields of view on the surface of the foil with a field of view of 100 μm×100 μm. Observation of the foil surface can use SIM (Scanning Ion Microscope) or SEM (Scanning Electron Microscope) to obtain the average crystal grain size based on JIS-H0501. However, the double crystal system is measured as different crystal grains.
<集合度> <Integration degree>
銅箔表面之由X射線繞射強度I(220)/I0(220)所表示之集合度為1.3以上且未達7.0。 The aggregation degree represented by the X-ray diffraction intensity I (220)/I 0 (220) on the surface of the copper foil is 1.3 or more and less than 7.0.
若集合度未達1.3，則厚度方向之蝕刻速度變小，銅箔之後述之蝕刻因子降低。於集合度成為7.0以上之應變速度之情形時，雖然蝕刻因子良好，但存在壓延銅箔之形狀變差而難以用作FPC用銅箔之情形。 If the degree of aggregation is less than 1.3, the etching rate in the thickness direction will decrease, and the etching factor described later on the copper foil will decrease. When the aggregation degree becomes a strain rate of 7.0 or more, although the etching factor is good, the shape of the rolled copper foil may deteriorate and it may be difficult to use it as a copper foil for FPC.
集合度係如下測定。首先，對於銅箔之壓延面，測定{220}面之X射線繞射強度，設為I(220)。 The aggregation degree is determined as follows. First, for the rolled surface of the copper foil, the X-ray diffraction intensity of the {220} surface is measured and set as I(220).
又，於同一條件下，對於純銅粉末(325mesh(JIS Z8801、純度99.5%)，於氫氣氣流中於300℃加熱1小時後使用)，測定{220}面之X射線繞射強度，設為I0(220)。 In addition, under the same conditions, for pure copper powder (325mesh (JIS Z8801, purity 99.5%), used after heating at 300°C for 1 hour in a hydrogen gas stream), the X-ray diffraction intensity of the {220} plane was measured and set as I 0 (220).
進而，如下標準化。 Furthermore, it is standardized as follows.
．{220}面集合度：I(220)/I0(220) . {220} Face set degree: I(220)/I 0 (220)
X射線繞射之測定條件如下。 The measurement conditions of X-ray diffraction are as follows.
．入射X射線源：Co、．加速電壓：25kV、．管電流：20mA、．發散狹縫：1度、．散射狹縫：1度、 ．光接收狹縫：0.3mm、．發散縱向限制狹縫：10mm、．單色光接收狹縫：0.8mm . Incident X-ray source: Co,. Accelerating voltage: 25kV,. Tube current: 20mA,. Divergence slit: 1 degree,. Scattering slit: 1 degree, . Light receiving slit: 0.3mm,. Divergence longitudinal restriction slit: 10mm,. Monochromatic light receiving slit: 0.8mm
<於300℃ 30分鐘之熱處理> <Heat treatment at 300℃ for 30 minutes>
本發明之銅箔係用於可撓性印刷基板，此時，積層銅箔與樹脂而成之CCL於200~400℃進行用以使樹脂硬化之熱處理，因此平均結晶粒徑、及由I(220)/I0(220)所表示之集合度變化。 The copper foil of the present invention is used for a flexible printed circuit board. In this case, the CCL formed by laminating copper foil and resin is heat-treated at 200 to 400°C to harden the resin. Therefore, the average crystal grain size is determined by I( 220)/I 0 (220) represents the change in the degree of aggregation.
因此，於與樹脂積層前後，平均結晶粒徑、及集合度變化。因此，本案之請求項1之可撓性印刷基板用銅箔規定了成為與樹脂積層後而成之覆銅積層體時之受到熱處理之狀態之銅箔。即，已受到熱處理，故而為不進行新的熱處理之狀態之銅箔。
Therefore, the average crystal grain size and the degree of aggregation change before and after lamination with the resin. Therefore, the copper foil for a flexible printed circuit board of
另一方面，本案之請求項1之可撓性印刷基板用銅箔規定了對與樹脂積層前之銅箔進行了上述熱處理時之狀態(例如，將熱處理前之銅箔線圈納入CCL之製造工場並積層於CCL時之經加熱之狀態)。該於300℃ 30分鐘之熱處理係模擬於CCL之積層時對樹脂進行硬化熱處理之溫度條件者。再者，為了防止熱處理所導致之銅箔表面之氧化，熱處理之環境較佳為還原性或非氧化性之環境，例如，只要設為真空環境或由氬氣、氮氣、氫氣、一氧化碳氣體等或者該等之混合氣體所構成之環境等即可。升溫速度只要為100~300℃/min之間即可。
On the other hand, the copper foil for flexible printed circuit boards in
本發明之銅箔例如可如下製造。首先，將銅錠熔解、鑄造後，熱軋，進行冷軋及退火，較佳為於冷軋時之初期進行再結晶退火，並且進行最終再結晶退火及最終冷軋，藉此可製造箔。 The copper foil of this invention can be manufactured as follows, for example. First, after melting and casting the copper ingot, hot rolling, cold rolling, and annealing are performed. Preferably, recrystallization annealing is performed at the initial stage of cold rolling, and final recrystallization annealing and final cold rolling are performed to produce foil.
藉由調整冷軋之總加工度η、最終冷軋前且最終再結晶退火後之平均結晶粒徑、及最終冷軋前之最終道次之應變速度，可控制平均結晶粒徑、及集合 度。 By adjusting the total processing degree η of cold rolling, the average crystal grain size before the final cold rolling and after the final recrystallization annealing, and the strain rate of the final pass before the final cold rolling, the average crystal grain size and aggregation can be controlled degree.
若將總加工度η設為6.10以上，則可更確實地增加由I(220)/I0(220)所表示之集合度。 If the total processing degree η is set to 6.10 or more, the aggregation degree represented by I(220)/I 0 (220) can be increased more reliably.
若將最終冷軋前且最終再結晶退火後之平均結晶粒徑設為5~20μm，則可確實地將製品之平均結晶粒徑設為0.5~4.0μm。 If the average crystal grain size before the final cold rolling and after the final recrystallization annealing is set to 5 to 20 μm, the average crystal grain size of the product can be reliably set to 0.5 to 4.0 μm.
若將最終冷軋前之最終道次之應變速度設為1000(/秒)以上，則可更確實地增加集合度。 If the strain rate of the final pass before the final cold rolling is set to 1000 (/sec) or more, the degree of aggregation can be increased more reliably.
<覆銅積層體及可撓性印刷基板> <Copper-clad laminate and flexible printed circuit board>
又，於本發明之銅箔上(1)塗膜(casting)樹脂前驅物(例如，被稱為清漆之聚醯亞胺前驅物)並施以熱使其聚合，(2)使用與基底膜同種之熱塑性接著劑將基底膜層疊於本發明之銅箔上，藉此獲得由銅箔與樹脂基材之2層所構成之覆銅積層體(CCL)。又，藉由在本發明之銅箔上層疊塗佈有接著劑之基底膜，而獲得由銅箔、樹脂基材、及該等之間之接著層之3層所構成之覆銅積層體(CCL)。該等CCL製造時，銅箔受到熱處理而再結晶。 In addition, on the copper foil of the present invention (1) coating (casting) resin precursor (for example, polyimide precursor called varnish) and applying heat to polymerize it, (2) using with base film The same kind of thermoplastic adhesive is laminated on the copper foil of the present invention with a base film to obtain a copper-clad laminate (CCL) composed of two layers of the copper foil and the resin substrate. Furthermore, by laminating a base film coated with an adhesive on the copper foil of the present invention, a copper-clad laminate consisting of three layers of copper foil, a resin base material, and an adhesive layer in between is obtained ( CCL). When these CCLs are manufactured, the copper foil is subjected to heat treatment to recrystallize.
於該等上使用光蝕刻法(photolithography)形成電路，視需要對電路實施鍍覆，層疊覆蓋膜(cover lay film)，藉此獲得可撓性印刷基板(可撓性配線板)。 A photolithography method is used to form a circuit on these, and the circuit is plated as necessary, and a cover lay film is laminated, thereby obtaining a flexible printed circuit board (flexible wiring board).
因此，本發明之覆銅積層體係積層銅箔與樹脂層而成。又，本發明之可撓性印刷基板係於覆銅積層體之銅箔上形成電路而成。 Therefore, the copper clad laminate system of the present invention is formed by laminating copper foil and resin layers. In addition, the flexible printed circuit board of the present invention is formed by forming a circuit on the copper foil of a copper-clad laminate.
作為樹脂層，可列舉PET(聚對苯二甲酸乙二酯)、PI(聚醯亞胺)、LCP(液晶聚合物)、PEN(聚萘二甲酸乙二酯)，然而並不限定於此。又，作為樹脂層，可使用該等之樹脂膜。 Examples of the resin layer include PET (polyethylene terephthalate), PI (polyimide), LCP (liquid crystal polymer), and PEN (polyethylene naphthalate), but it is not limited to these . Moreover, as the resin layer, these resin films can be used.
作為樹脂層與銅箔之積層方法，可於銅箔之表面塗佈成為樹脂層之材料並加熱成膜。又，使用樹脂膜作為樹脂層，可於樹脂膜與銅箔之間使用以下接著劑，亦可不使用接著劑而將樹脂膜熱壓接於銅箔。然而，自不對樹脂膜施加多 餘之熱之方面而言，較佳為使用接著劑。 As a layering method of the resin layer and the copper foil, the material that becomes the resin layer can be coated on the surface of the copper foil and heated to form a film. In addition, a resin film is used as a resin layer, and the following adhesive may be used between the resin film and the copper foil, or the resin film may be thermocompression-bonded to the copper foil without using the adhesive. However, since it does not apply too much to the resin film In terms of residual heat, it is preferable to use an adhesive.
於使用膜作為樹脂層之情形時，將該膜經由接著劑層積層於銅箔即可。於該情形時，較佳為使用與膜為相同成分之接著劑。例如，於使用聚醯亞胺膜作為樹脂層之情形時，較佳為接著劑層亦使用聚醯亞胺系接著劑。再者，此處所謂之聚醯亞胺接著劑係指包含醯亞胺鍵之接著劑，亦包含聚醚醯亞胺等。 When using a film as a resin layer, what is necessary is just to laminate this film on copper foil via an adhesive layer. In this case, it is preferable to use an adhesive having the same composition as the film. For example, when a polyimide film is used as the resin layer, it is preferable that the adhesive layer also uses a polyimide-based adhesive. Furthermore, the polyimine adhesive referred to herein refers to an adhesive containing an imine bond, and also includes polyetherimine and the like.
再者，本發明並不限定於上述實施形態。又，只要發揮本發明之作用效果，則上述實施形態之銅合金亦可含有其他成分。又，亦可為電解銅箔。 In addition, the present invention is not limited to the above-mentioned embodiment. In addition, as long as the effect of the present invention is exerted, the copper alloy of the above-mentioned embodiment may contain other components. Moreover, it may be an electrolytic copper foil.
例如，可對銅箔之表面實施粗化處理、防銹處理、耐熱處理、或該等之組合之表面處理。 For example, the surface of the copper foil may be roughened, rust-proof, heat-resistant, or a combination of these.
[實施例] [Example]
其次，列舉實施例對本發明更詳細地進行說明，但本發明並不限定於該等。於電解銅中分別添加表1所示之元素設為表1所示之組成，於Ar環境下進行鑄造獲得鑄錠。鑄錠中之氧含量未達15ppm。將該鑄錠於900℃均質化退火後，熱軋，其後反覆進行冷軋及再結晶退火，進而進行最終再結晶退火及最終冷軋，獲得壓延銅箔。 Next, the present invention will be explained in more detail with examples, but the present invention is not limited to these. The elements shown in Table 1 were added to the electrolytic copper to set the composition shown in Table 1, and the ingots were obtained by casting in an Ar environment. The oxygen content in the ingot does not reach 15 ppm. After homogenization annealing of the ingot at 900° C., hot rolling, cold rolling and recrystallization annealing are repeated thereafter, and final recrystallization annealing and final cold rolling are further performed to obtain rolled copper foil.
對所得之壓延銅箔於氬氣環境下實施300℃×30分鐘之熱處理，獲得銅箔樣本。熱處理後之銅箔模擬於CCL之積層時受到熱處理之狀態。 The obtained rolled copper foil was subjected to a heat treatment at 300° C.×30 minutes in an argon atmosphere to obtain a copper foil sample. The heat-treated copper foil simulates the state of being heat-treated during the lamination of CCL.
<銅箔樣本之評價> <Evaluation of Copper Foil Samples>
1.導電率 1. Conductivity
對於上述熱處理後之各銅箔樣本，基於JIS H 0505藉由4端子法測定25℃之導電率(%IACS)。 For each copper foil sample after the above heat treatment, the electrical conductivity (%IACS) at 25°C was measured by the 4-terminal method based on JIS H 0505.
若導電率大於80%IACS，則導電性良好。 If the conductivity is greater than 80% IACS, the conductivity is good.
2.集合度 2. Aggregation degree
對於上述熱處理後之各銅箔樣本，使用X射線繞射裝置(RINT-2500：理學電機製造)藉由上述方法測定集合度。再者，除由I(220)/I0(220)所表示之集合度以外，同樣地測定{200}面之X射線繞射強度，亦求出I(200)/I0(200)。 For each copper foil sample after the above heat treatment, an X-ray diffraction device (RINT-2500: manufactured by Rigaku Electric) was used to measure the aggregation degree by the above method. Furthermore, in addition to the degree of aggregation represented by I(220)/I 0 (220), the X-ray diffraction intensity of the {200} plane is measured in the same way, and I(200)/I 0 (200) is also obtained.
3.蝕刻因子EF 3. Etching factor EF
將銅箔與樹脂貼合，其後將乾膜抗蝕劑層壓於銅箔表面，於抗蝕劑上形成短條狀(L/S=25/25)之電路圖案。藉由氯化銅蝕刻劑之噴霧蝕刻改變蝕刻時間而實施蝕刻。 The copper foil and the resin are bonded together, and then the dry film resist is laminated on the surface of the copper foil to form a short strip (L/S=25/25) circuit pattern on the resist. The etching is performed by changing the etching time by spray etching of copper chloride etchant.
EF之測定方法存在多種，於本發明中，藉由作為蝕刻因子EF之最普通之求出方法，即，以相對於寬度方向之深度方向之蝕刻速度進行評價。於本發明中，如圖1、圖2所示進行測定。再者，下述式(1)僅著眼於深度方向及寬度方向之蝕刻速度，不考慮傾斜方向之蝕刻速度。 There are many methods for measuring EF. In the present invention, the most common method for obtaining the etching factor EF is to evaluate the etching rate in the depth direction relative to the width direction. In the present invention, the measurement is performed as shown in Figs. 1 and 2. In addition, the following formula (1) focuses only on the etching rate in the depth direction and the width direction, and does not consider the etching rate in the oblique direction.
EF如圖1所示，由1條電路之剖面之寬度方向及深度方向之蝕刻速度由下式(1)求出。 As shown in Fig. 1, EF is calculated by the following formula (1) from the etching rate in the width direction and the depth direction of the cross section of a circuit.
EF=深度方向之蝕刻速度/寬度方向之蝕刻速度(1) EF=Etching speed in the depth direction/etching speed in the width direction(1)
然而，由於蝕刻速度本身之測定較為困難，故分別測定改變蝕刻時間時之電路之寬度及深度。繼而，如圖2所示，將橫軸設為電路之寬度，將縱軸設為電路之深度，對各資料進行繪圖，由下式(2)近似地求出。即，由利用最小平方法之一次之近似式求出圖2之曲線圖之斜率作為EF。 However, since it is difficult to measure the etching rate itself, the width and depth of the circuit when the etching time is changed are measured separately. Then, as shown in FIG. 2, the horizontal axis is set as the width of the circuit, and the vertical axis is set as the depth of the circuit, and each data is plotted, and it is approximated by the following formula (2). That is, the slope of the graph in Fig. 2 is obtained from the first-order approximation formula using the least square method as EF.
EF≒深度之時間變化/(寬度之時間變化/2)=2×深度之時間變化/寬度之時間變化(2) EF≒Time change of depth/(time change of width/2)=2×time change of depth/time change of width(2)
此處，式(2)之係數「2」由於寬度方向之蝕刻於圖1之左右兩側進行，故必須減半。 Here, the coefficient "2" of the formula (2) must be halved because the etching in the width direction is performed on the left and right sides of FIG. 1.
繼而，根據EF之值按照以下指標進行評價。若評價為◎、○，則良好。 Then, based on the value of EF, the following indicators are used for evaluation. If the evaluation is ⊚, ○, it is good.
◎：EF為1.4以上 ◎: EF is 1.4 or more
×：EF為1.1以上且未達1.4 ×: EF is 1.1 or more and less than 1.4
×：EF未達1.1 ×: EF less than 1.1
4.軟蝕刻性 4. Soft etching
對於上述熱處理後之各銅箔樣本，於以下條件下對表面進行軟蝕刻。作為評價軟蝕刻性之指標，對軟蝕刻後之銅箔表面之基於JIS-B0601(2001)之算術平均粗糙度Ra進行測定。 For each copper foil sample after the above heat treatment, the surface was soft-etched under the following conditions. As an index for evaluating soft etching properties, the arithmetic average roughness Ra of the copper foil surface after soft etching was measured based on JIS-B0601 (2001).
作為軟蝕刻條件，模擬用於賦予銅箔與抗蝕劑之密接性之軟蝕刻，將銅箔於過硫酸鈉濃度100g/L、過氧化氫濃度35g/L之水溶液(液溫25℃)中浸漬420秒。將算術平均粗糙度Ra為0.2μm以下之情形視為軟蝕刻性良好(○)，將算術平均粗糙度Ra超過0.2μm之情形視為軟蝕刻性不良(×)。 As the soft etching conditions, simulate soft etching for imparting adhesion between copper foil and resist, and put the copper foil in an aqueous solution (liquid temperature 25°C) with a sodium persulfate concentration of 100g/L and a hydrogen peroxide concentration of 35g/L Immerse for 420 seconds. The case where the arithmetic average roughness Ra is 0.2 μm or less is regarded as good soft etching properties (○), and the case where the arithmetic average roughness Ra exceeds 0.2 μm is regarded as poor soft etching properties (×).
若於軟蝕刻後抗蝕劑良好地追隨銅箔表面，則密接性優異，電路圖案之精度提高，軟蝕刻性變良好。若Ra超過0.2μm，則抗蝕劑難以追隨銅箔表面，抗蝕劑與銅箔表面之間易產生間隙。而且，因蝕刻液侵入該間隙導致電路圖案之形成時之精度降低。 If the resist follows the surface of the copper foil well after soft etching, the adhesiveness is excellent, the accuracy of the circuit pattern is improved, and the soft etching property becomes good. If Ra exceeds 0.2 μm, it is difficult for the resist to follow the surface of the copper foil, and a gap is likely to occur between the resist and the surface of the copper foil. In addition, the etching liquid invades the gap, which reduces the accuracy of circuit pattern formation.
5.結晶粒徑 5. Crystal size
對於上述熱處理後之各銅箔樣本，使用SEM(Scanning Electron Microscope)對壓延面進行觀察，基於JIS H 0501求出平均粒徑。然而，雙晶係看作不同之晶粒進行測定。測定區域係設為平行於壓延方向之剖面之400μm×400μm。 For each copper foil sample after the above heat treatment, the rolled surface was observed using SEM (Scanning Electron Microscope), and the average particle size was determined based on JIS H 0501. However, the double crystal system is measured as different crystal grains. The measurement area is set to be 400 μm×400 μm in a cross section parallel to the rolling direction.
將所得之結果表示於表1、表2。 The results obtained are shown in Table 1 and Table 2.
自表1、表2可知，於結晶粒徑為0.5~4.0μm、且由I(220)/I0(220)所表示之集合度為1.3以上且未達7.0之各實施例之情形時，蝕刻因子及 軟蝕刻性均優異。藉此，於銅箔整個面可獲得均勻之電路圖案而良率提高，進而使電路微細化時電路圖案之精度提高。 It can be seen from Table 1 and Table 2 that when the crystal grain size is 0.5 to 4.0 μm, and the aggregation degree represented by I(220)/I 0 (220) is 1.3 or more and less than 7.0 in each embodiment, Both the etching factor and soft etching properties are excellent. Thereby, a uniform circuit pattern can be obtained on the entire surface of the copper foil, and the yield rate is improved, thereby improving the accuracy of the circuit pattern when the circuit is miniaturized.
於最終冷軋之最終道次之應變速度未達1000(s-1)之比較例1~4之情形時，集合度未達1.3，雖然軟蝕刻性良好，但蝕刻因子降低。因此，於使電路微細化時，電路圖案之精度降低。 In the case of Comparative Examples 1 to 4 in which the strain rate of the final pass of the final cold rolling did not reach 1000 (s-1), the aggregation degree did not reach 1.3, and although the soft etching performance was good, the etching factor was lowered. Therefore, when the circuit is miniaturized, the accuracy of the circuit pattern is reduced.
於最終冷軋前且最終再結晶退火後之平均結晶粒徑超過20μm之比較例5之情形時，製品之平均結晶粒徑超過4.0μm，雖然蝕刻因子良好，但軟蝕刻性較差。因此，於銅箔整個面無法獲得均勻之電路圖案而良率降低。 In the case of Comparative Example 5 where the average crystal grain size before the final cold rolling and after the final recrystallization annealing exceeds 20 μm, the average crystal grain size of the product exceeds 4.0 μm. Although the etching factor is good, the soft etching property is poor. Therefore, a uniform circuit pattern cannot be obtained on the entire surface of the copper foil, and the yield is reduced.
於總加工度未達6.10之比較例6之情形時，集合度未達1.3，蝕刻因子降低。 In the case of Comparative Example 6 in which the total processing degree did not reach 6.10, the aggregation degree did not reach 1.3, and the etching factor decreased.
於添加元素之合計含量超過0.7質量%之比較例7之情形時，導電率未達80%，導電性較差。 In the case of Comparative Example 7 in which the total content of the added elements exceeded 0.7% by mass, the electrical conductivity did not reach 80%, and the electrical conductivity was poor.
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| JPJP2018-008117 | 2018-01-22 | ||
| JP2018008117A JP6793138B2 (en) | 2018-01-22 | 2018-01-22 | Copper foil for flexible printed circuit boards, copper-clad laminates using it, flexible printed circuit boards, and electronic devices |
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| JP7164752B1 (en) * | 2022-07-14 | 2022-11-01 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic equipment |
| JP7194857B1 (en) | 2022-07-14 | 2022-12-22 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic equipment |
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| JP2004256879A (en) * | 2003-02-27 | 2004-09-16 | Nikko Metal Manufacturing Co Ltd | Rolled copper foil having high elongation |
| TW201738393A (en) * | 2016-01-15 | 2017-11-01 | Jx Nippon Mining & Metals Corp | Copper Foil, Copper-Clad Laminate Board, Method For Producing Printed Wiring Board, Method For Producing Electronic Apparatus, Method For Producing Transmission Channel, And Method For Producing Antenna |
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| JP3962291B2 (en) * | 2001-07-17 | 2007-08-22 | 日鉱金属株式会社 | Rolled copper foil for copper clad laminate and method for producing the same |
| JP5055088B2 (en) * | 2007-10-31 | 2012-10-24 | Ｊｘ日鉱日石金属株式会社 | Copper foil and flexible printed circuit board using the same |
| JP2013142162A (en) * | 2012-01-10 | 2013-07-22 | Mitsubishi Shindoh Co Ltd | Copper or copper alloy plate for base plate with excellent warp workability, and method for producing the same |
| JP6360654B2 (en) * | 2012-01-17 | 2018-07-18 | Ｊｘ金属株式会社 | Rolled copper foil for flexible printed wiring boards |
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| JP6392268B2 (en) * | 2016-02-05 | 2018-09-19 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
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| JP2004256879A (en) * | 2003-02-27 | 2004-09-16 | Nikko Metal Manufacturing Co Ltd | Rolled copper foil having high elongation |
| TW201738393A (en) * | 2016-01-15 | 2017-11-01 | Jx Nippon Mining & Metals Corp | Copper Foil, Copper-Clad Laminate Board, Method For Producing Printed Wiring Board, Method For Producing Electronic Apparatus, Method For Producing Transmission Channel, And Method For Producing Antenna |
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