TW201734219A - Copper foil for flexible printed circuit board, cooper-clad laminate using same, flexible printed circuit board, and electronic machine whose copper foil contains 0.001~0.05 mass% of Ag and contains total 0.003~0.825 mass% of addition elements selected from more than one of the group of P, Ti, Sn, Ni, Be, Zn, In, and Mg - Google Patents
Copper foil for flexible printed circuit board, cooper-clad laminate using same, flexible printed circuit board, and electronic machine whose copper foil contains 0.001~0.05 mass% of Ag and contains total 0.003~0.825 mass% of addition elements selected from more than one of the group of P, Ti, Sn, Ni, Be, Zn, In, and Mg Download PDFInfo
- Publication number
- TW201734219A TW201734219A TW105143778A TW105143778A TW201734219A TW 201734219 A TW201734219 A TW 201734219A TW 105143778 A TW105143778 A TW 105143778A TW 105143778 A TW105143778 A TW 105143778A TW 201734219 A TW201734219 A TW 201734219A
- Authority
- TW
- Taiwan
- Prior art keywords
- copper foil
- circuit board
- flexible printed
- printed circuit
- copper
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Abstract
Description
本發明係關於一種適用於可撓性印刷基板等之配線構件的銅箔、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 which is applied to a wiring member 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，故被廣泛地使用於電子電路之彎折部分或可動部分。例如，於HDD或DVD及CD-ROM等光碟相關機器之可動部分或折疊式行動電話之彎折部分等使用有FPC。 Since a flexible printed circuit board (flexible wiring board, hereinafter referred to as "FPC") has flexibility, it is widely used in a bent portion or a movable portion of an electronic circuit. For example, an FPC is used for a movable portion of a disc-related machine such as an HDD or a DVD or a CD-ROM or a bent portion of a foldable mobile phone.
FPC係如下者：藉由對積層有銅箔與樹脂之Copper Clad Laminate(覆銅積層體，以下稱為CCL)進行蝕刻，而形成配線，再以被稱為覆蓋層(cover lay)之樹脂層被覆於其上。於積層覆蓋層之前一階段，進行銅箔表面之蝕刻，作為用以提升銅箔與覆蓋層之密接性的表面改質步驟之一環。又，為了減少銅箔之厚度使彎曲性提升，亦會有進行減厚蝕刻之情形。 The FPC is a method in which a wiring is formed by etching Copper Clad Laminate (hereinafter referred to as CCL) in which a copper foil and a resin are laminated, and a resin layer called a cover lay-up is formed. Covered on it. The copper foil surface is etched at a stage before the buildup of the overcoat layer as one of the surface modification steps for improving the adhesion between the copper foil and the cover layer. Further, in order to reduce the thickness of the copper foil and improve the flexibility, there is a case where the thick etching is performed.
再者，隨著電子機器之小型、薄型、高性能化，而要求於此等機器之內部以高密度構裝FPC，但為了進行高密度構裝，需要將FPC彎折放置於經小型化之機器的內部，亦即需要高彎折性。 Furthermore, with the small size, thinness, and high performance of electronic devices, it is required to construct FPCs at high density inside such devices. However, in order to perform high-density mounting, FPCs need to be bent and placed in a miniaturized manner. The inside of the machine, that is, the need for high bending.
另一方面，改善以IPC彎曲性所代表之高循環彎曲性的銅箔不斷地被開發(專利文獻1、2)。 On the other hand, copper foil which improves the high cycle bending property represented by the IPC bendability has been continuously developed (Patent Documents 1 and 2).
專利文獻1：日本特開2010-100887號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-100887
專利文獻2：日本特開2009-111203號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2009-111203
然而，如上述般為了以高密度構裝FPC，需要提升以MIT抗折性所代表之彎折性，於以往之銅箔，具有彎折性未獲得充分改善之問題。 However, in order to mount the FPC at a high density as described above, it is necessary to improve the bending property represented by the MIT folding resistance, and the conventional copper foil has a problem that the bending property is not sufficiently improved.
又，隨著電子機器之小型、薄型、高性能化，FPC之電路寬度、間隔寬度亦微細化至20~30μm左右，當藉由蝕刻形成電路時，會有蝕刻因子(etching factor)或電路直線性容易劣化之問題，亦要求將其解決。 Moreover, with the small size, thinness, and high performance of the electronic device, the circuit width and the interval width of the FPC are also reduced to about 20 to 30 μm. When the circuit is formed by etching, there is an etching factor or a circuit straight line. The problem of easy deterioration of sex is also required to be solved.
本發明係為了解決上述之課題而完成者，目的在於提供一種彎折性及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。 In order to solve the problems described above, the present invention has been made to provide a copper foil for a flexible printed circuit board having excellent flexibility and etchability, a copper-clad laminate using the same, a flexible printed circuit board, and an electronic device.
本發明人等經各種研究後之結果，發現藉由將銅箔再結晶後之晶粒微細化，可提高強度且提升彎折性。其係由於越藉由霍爾-貝曲(Hall-Petch)法則將晶粒微細化，強度會變得越高，彎折性亦會變得越高。惟，若將晶粒太過微細化，則強度會變得過高，彎曲剛性變大，彈回量(spring back)變大而不適於可撓性印刷基板用途。因此，亦規定結晶粒徑之範圍。 As a result of various studies, the present inventors have found that by refining the crystal grains after recrystallization of the copper foil, the strength can be improved and the bending property can be improved. In this case, the grain size is made finer by the Hall-Petch rule, and the strength is increased, and the bending property is also increased. However, when the crystal grains are too fine, the strength is too high, the bending rigidity is increased, and the spring back is increased, which is not suitable for the use of the flexible printed circuit board. Therefore, the range of the crystal grain size is also specified.
又，藉由將結晶粒徑微細化至近年來之FPC之20~30μm左右之電路寬度的約1/10左右，亦可改善藉由蝕刻形成電路時之蝕刻因子或電路直線性。 Further, by refining the crystal grain size to about 1/10 of the circuit width of about 20 to 30 μm of the FPC in recent years, the etching factor or the circuit linearity when the circuit is formed by etching can be improved.
亦即，本發明之可撓性印刷基板用銅箔，相對於以JIS- H3100(C1100)規定之精銅或JIS-H3100(C1011)之無氧銅，含有0.001~0.05質量%之Ag，且含有合計0.003~0.825質量%之選自P、Ti、Sn、Ni、Be、Zn、In及Mg之群中的1種以上之添加元素而成，平均結晶粒徑為0.5~4.0μm，且拉伸強度為235~290MPa。 That is, the copper foil for a flexible printed circuit board of the present invention is relative to JIS- The refined copper specified by H3100 (C1100) or the oxygen-free copper of JIS-H3100 (C1011) contains 0.001 to 0.05% by mass of Ag, and contains 0.003 to 0.825% by mass of a total selected from P, Ti, Sn, Ni, Be, The additive element is one or more selected from the group consisting of Zn, In, and Mg, and has an average crystal grain size of 0.5 to 4.0 μm and a tensile strength of 235 to 290 MPa.
於本發明之可撓性印刷基板用銅箔，較佳為，前述銅箔為壓延銅箔，於300℃進行30分鐘熱處理後之前述平均結晶粒徑為0.5~4.0μm，且前述拉伸強度為235~290MPa。 In the copper foil for a flexible printed circuit board of the present invention, it is preferable that the copper foil is a rolled copper foil, and the average crystal grain size after heat treatment at 300 ° C for 30 minutes is 0.5 to 4.0 μm, and the tensile strength is the same. It is 235~290MPa.
將厚度25μm之聚醯亞胺樹脂膜積層於前述銅箔之單面而成的覆銅積層體，以彎曲半徑為0.05mm且前述銅箔成為外側之方式作180度密接彎曲，然後將彎折部分恢復至0度，重複此測試3次後，以倍率200觀察前述銅箔時，較佳為未目視辨認到裂紋。 A copper-clad laminate obtained by laminating a polyimide film having a thickness of 25 μm on one side of the copper foil is bent at 180 degrees so that the bending radius is 0.05 mm, and the copper foil is outwardly bent, and then bent. When the copper foil was observed at a magnification of 200, it was preferred that the crack was not visually recognized.
本發明之覆銅積層體，係將前述可撓性印刷基板用銅箔與樹脂層積層而成。 In the copper clad laminate according to the present invention, the copper foil for a flexible printed circuit board and a resin layer are laminated.
本發明之可撓性印刷基板係使用前述覆銅積層體，於前述銅箔形成電路而成。 In the flexible printed circuit board of the present invention, the copper clad laminate is used, and the copper foil is formed into a circuit.
前述電路之L/S較佳為40/40~15/15(μm/μm)。另，電路之L/S(Line and Space)係指構成電路之配線的寬度(L：Line)與相鄰之配線的間隔(S：Space)之比。L採用電路中之L的最小值，S採用電路中之S的最小值。 The L/S of the aforementioned circuit is preferably 40/40 to 15/15 (μm/μm). In addition, the line/space of the circuit refers to the ratio of the width (L: Line) of the wiring constituting the circuit to the interval (S: Space) of the adjacent wiring. L takes the minimum value of L in the circuit, and S takes the minimum value of S in the circuit.
另，L及S只要為15~40μm即可，兩者無須為相同之值。例如，亦可取L/S=20.5/35、35/17等值。 In addition, L and S may be 15 to 40 μm, and the two need not be the same value. For example, values such as L/S=20.5/35 and 35/17 may also be taken.
本發明之電子機器係使用前述可撓性印刷基板而成。 The electronic device of the present invention is formed using the above-described flexible printed circuit board.
若根據本發明，則獲得彎折性及蝕刻性優異之可撓性印刷基板用銅箔。 According to the present invention, a copper foil for a flexible printed circuit board having excellent bending properties and etching properties is obtained.
10‧‧‧壓縮測試機 10‧‧‧Compression test machine
10a‧‧‧下模具 10a‧‧‧Mold
10b‧‧‧上模具 10b‧‧‧Upper mold
20‧‧‧板 20‧‧‧ board
30‧‧‧CCL樣品 30‧‧‧CCL samples
30s‧‧‧彎折前端部 30s‧‧‧Bent front end
圖1係顯示CCL之彎折性測試方法之圖。 Figure 1 is a diagram showing the bending test method of CCL.
以下，說明本發明之銅箔的實施形態。另，於本發明中%只要無特別說明，皆表示質量%。 Hereinafter, an embodiment of the copper foil of the present invention will be described. Further, % in the present invention means % by mass unless otherwise specified.
<組成> <composition>
本發明之銅箔，相對於以JIS-H3100(C1100)規定之精銅或JIS-H3100(C1011)之無氧銅，含有0.001~0.05質量%之Ag，且含有合計0.003~0.825質量%之選自P、Ti、Sn、Ni、Be、Zn、In及Mg之群中的1種以上之添加元素而成。 The copper foil of the present invention contains 0.001 to 0.05% by mass of Ag, and contains a total of 0.003 to 0.825% by mass, based on the refined copper specified in JIS-H3100 (C1100) or the oxygen-free copper of JIS-H3100 (C1011). It is formed from one or more kinds of added elements in the group of P, Ti, Sn, Ni, Be, Zn, In, and Mg.
如上述般，於本發明中，藉由將銅箔再結晶後之晶粒微細化，來提高強度且提升彎折性。 As described above, in the present invention, by refining the crystal grains after recrystallization of the copper foil, the strength is improved and the bending property is improved.
惟，為了更確實地進行晶粒之微細化，於冷壓延時之初期僅進行一次再結晶退火，之後較佳不進行再結晶退火。藉此，藉由冷壓延大量導入加工應變，產生動態再結晶，而可確實地實現晶粒之微細化。 However, in order to more accurately refine the crystal grains, only one recrystallization annealing is performed at the initial stage of the cold pressing delay, and thereafter, recrystallization annealing is preferably not performed. Thereby, the processing strain is introduced in a large amount by cold rolling, and dynamic recrystallization is generated, and the grain refinement can be surely achieved.
又，當要增大冷壓延中之加工應變時，作為於最後冷壓延(於反覆進行退火與壓延之步驟整體中，於最後之退火後進行之精加工壓延)之加工度，若η=ln(最後冷壓延前之板厚/最後冷壓延後之板厚)=3.5~7.5，則較佳。 Further, when the processing strain in the cold rolling is to be increased, the degree of processing as the final cold rolling (finishing calendering after the final annealing in the entire step of annealing and calendering repeatedly), if η = ln (The thickness of the plate before the final cold rolling / the thickness of the plate after the final cold rolling) = 3.5 to 7.5, which is preferable.
當η未達3.5之情形時，由於加工時之應變的累積少，再結晶粒之核變 少，因此會有再結晶粒變粗大之傾向。當η大於7.5之情形時，應變會過量累積，成為晶粒成長之驅動力，而會有晶粒變粗大之傾向。若η=5.5~7.5，則更佳。 When η is less than 3.5, the nucleation of recrystallized grains is less due to less accumulation of strain during processing. Since there are few, there is a tendency that the recrystallized grains become coarse. When η is larger than 7.5, the strain excessively accumulates, which becomes a driving force for grain growth, and tends to coarsen the crystal grains. If η = 5.5~7.5, it is better.
又，若含有Ag及上述添加元素作為使晶粒微細化之添加元素，則於冷壓延時可使差排密度增加，確實地實現晶粒之微細化。 In addition, when Ag and the above-mentioned additive element are added as an additive element for refining crystal grains, the difference in the discharge density can be increased in the cold press delay, and the grain size can be surely made fine.
其中，Ag會使再結晶粒徑對於再結晶退火條件之感受性降低。亦即如後述般，於CCL積層時會進行用以使樹脂硬化之熱處理，但實際上熱處理之溫度、時間會變動，升溫速度亦會因製造裝置或製造者等而有所不同。因此，因熱處理而會有使銅箔之再結晶粒的粒徑變大之虞。於是，藉由含有Ag，即使CCL積層時之熱處理條件有改變，亦可穩定地對晶粒進行微細化。 Among them, Ag lowers the sensitivity of the recrystallized grain size to recrystallization annealing conditions. That is, as will be described later, heat treatment for curing the resin is performed at the time of CCL lamination, but actually, the temperature and time of the heat treatment fluctuate, and the temperature increase rate also differs depending on the manufacturing apparatus or the manufacturer. Therefore, the particle size of the recrystallized grains of the copper foil is increased by heat treatment. Then, by containing Ag, even if the heat treatment conditions at the time of CCL lamination are changed, the crystal grains can be stably refined.
Ag之含量若未達0.001質量%，則難以進行晶粒之微細化。又，Ag之含量若超過0.05質量%，則有時再結晶溫度會上升，當與樹脂積層時不會再結晶，強度變得過高，銅箔及CCL之彎折性會劣化。 When the content of Ag is less than 0.001% by mass, it is difficult to refine the crystal grains. In addition, when the content of Ag exceeds 0.05% by mass, the recrystallization temperature may increase, and when it is laminated with the resin, it will not recrystallize, and the strength will become too high, and the bending property of the copper foil and CCL may deteriorate.
上述添加元素之合計含量若未達0.003質量%，則晶粒之微細化會難以進行，若超過0.825質量%，則有時導電率會下降。又，有時再結晶溫度會上升，當與樹脂積層時不會再結晶，強度變得過高，銅箔及CCL之彎折性會劣化。。 When the total content of the above-mentioned additive elements is less than 0.003 mass%, it is difficult to refine the crystal grains, and if it exceeds 0.825 mass%, the electrical conductivity may be lowered. Further, the recrystallization temperature may increase, and when it is laminated with the resin, it will not recrystallize, and the strength will become too high, and the bending property of the copper foil and the CCL may deteriorate. .
<平均結晶粒徑> <Average crystal grain size>
銅箔之平均結晶粒徑為0.5~4.0μm。平均結晶粒徑若未達0.5μm，則強度會變得過高，彎曲剛性變大，彈回量變大而不適於可撓性印刷基板用途。平均結晶粒徑若超過4.0μm，則無法實現晶粒之微細化，提高強度使 彎折性提升會變得困難，且蝕刻因子或電路直線性會劣化，蝕刻性降低。 The average crystal grain size of the copper foil is 0.5 to 4.0 μm. When the average crystal grain size is less than 0.5 μm, the strength is too high, the bending rigidity is increased, and the amount of rebound is increased, which is not suitable for the use of the flexible printed circuit board. When the average crystal grain size exceeds 4.0 μm, the grain size cannot be made fine, and the strength is improved. The improvement in bending property becomes difficult, and the etching factor or the linearity of the circuit is deteriorated, and the etching property is lowered.
平均結晶粒徑之測量，為了避免誤差，而以100μm×100μm之視域對箔表面觀察3視域以上來進行。箔表面之觀察，可使用SIM(Scanning Ion Microscope，掃描離子顯微鏡)或SEM(Scanning Electron Microscope，掃描式電子顯微鏡)，依照JIS H 0501求出平均結晶粒徑。 The measurement of the average crystal grain size was carried out by observing the surface of the foil at a viewing angle of 3 or more in a field of view of 100 μm × 100 μm in order to avoid an error. The average crystal grain size can be determined in accordance with JIS H 0501 using a SIM (Scanning Ion Microscope) or a SEM (Scanning Electron Microscope).
惟，雙晶視為各別之晶粒來測量。 However, twins are considered as separate grains to measure.
<拉伸強度(TS)> <tensile strength (TS)>
銅箔之拉伸強度為235~290MPa。如上述般，將晶粒微細化，藉此提升拉伸強度。拉伸強度若未達235MPa，則提高強度使彎折性提升會變得困難。拉伸強度若超過290MPa，則強度會變得過高，彎曲剛性變大，彈回量變大而不適於可撓性印刷基板用途。 The tensile strength of the copper foil is 235 to 290 MPa. As described above, the crystal grains are refined to thereby increase the tensile strength. If the tensile strength is less than 235 MPa, it is difficult to increase the strength and increase the bending property. When the tensile strength exceeds 290 MPa, the strength is too high, the bending rigidity is increased, and the amount of rebound is increased, which is not suitable for the use of a flexible printed circuit board.
拉伸強度藉由依據IPC-TM650之拉伸測試，以測試片寬度12.7mm，室溫(15~35℃)，拉伸速度50.8mm/min，量規長度50mm，於與銅箔之壓延方向平行的方向進行拉伸測試來測量。 Tensile strength by tensile test according to IPC-TM650, test piece width 12.7mm, room temperature (15~35 °C), tensile speed 50.8mm/min, gauge length 50mm, in the direction of rolling with copper foil The tensile test is performed in parallel directions to measure.
<於300℃進行30分鐘熱處理> <30 minutes heat treatment at 300 ° C>
於300℃對銅箔進行30分鐘熱處理後之平均結晶粒徑可為0.5~4.0μm，且拉伸強度可為235~290MPa。 The average crystal grain size after heat treatment of the copper foil at 300 ° C for 30 minutes may be 0.5 to 4.0 μm, and the tensile strength may be 235 to 290 MPa.
本發明之銅箔係使用於可撓性印刷基板，此時，積層有銅箔與樹脂之CCL由於會以200~400℃進行用以使樹脂硬化之熱處理，因此晶粒可能會因再結晶而粗大化。 The copper foil of the present invention is used for a flexible printed circuit board. In this case, since the CCL in which the copper foil and the resin are laminated is subjected to heat treatment for hardening the resin at 200 to 400 ° C, the crystal grains may be recrystallized. Coarse.
因此，於與樹脂積層之前後，銅箔之平均結晶粒徑及拉伸強度會改變。於是，本案請求項1之可撓性印刷基板用銅箔，規定「變成與樹脂積層後 的覆銅積層體之後，樹脂受硬化熱處理後之狀態的銅箔」。 Therefore, the average crystal grain size and tensile strength of the copper foil change after the layer is laminated with the resin. Therefore, the copper foil for a flexible printed circuit board of claim 1 of the present invention is defined as "becoming laminated with resin. After the copper-clad laminate, the resin is subjected to a hardened heat-treated copper foil.
另一方面，本案請求項2之可撓性印刷基板用銅箔，則規定「對與樹脂積層前之銅箔進行過上述熱處理時的狀態」。此於300℃進行30分鐘之熱處理，係仿造CCL積層時將樹脂硬化熱處理之溫度條件者。 On the other hand, the copper foil for a flexible printed circuit board of claim 2 is defined as "a state in which the copper foil before the resin layer is subjected to the above heat treatment". This is a heat treatment at 300 ° C for 30 minutes, which is a temperature condition in which the resin is hardened and heat-treated when the CCL laminate is formed.
本發明之銅箔，例如可如下述般進行製造。首先，可將上述添加物添加於銅鑄錠，進行熔解、鑄造後，進行熱壓延，再進行冷壓延與退火，進行上述之最後冷壓延，藉此來製造箔。 The copper foil of the present invention can be produced, for example, as follows. First, the additive may be added to a copper ingot, melted and cast, and then hot rolled, cold rolled and annealed, and subjected to the above-described final cold rolling to produce a foil.
<覆銅積層體及可撓性印刷基板> <Copper-clad laminate and flexible printed substrate>
又，(1)將樹脂前驅物(例如被稱為清漆之聚醯亞胺前驅物)塗膜(casting)於本發明之銅箔並施加熱使之聚合，(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，藉此可得到由銅箔與樹脂基材2層構成之覆銅積層體(CCL)。又，將塗布有接著劑之基底膜層疊於本發明之銅箔，藉此可得到由銅箔與樹脂基材與其間之接著層3層構成的覆銅積層體(CCL)。於此等之CCL製造時，銅箔會受到熱處理而再結晶化。 Further, (1) a resin precursor (for example, a polyimide precursor known as varnish) is cast on the copper foil of the present invention and heat is applied to polymerize it, and (2) the same species as the base film is used. In the thermoplastic adhesive, a base film is laminated on the copper foil of the present invention, whereby a copper clad laminate (CCL) composed of two layers of a copper foil and a resin substrate can be obtained. Further, a base film coated with an adhesive is laminated on the copper foil of the present invention, whereby a copper clad laminate (CCL) composed of a copper foil and a resin substrate and an adhesive layer therebetween can be obtained. At the time of production of such CCL, the copper foil is subjected to heat treatment and recrystallized.
將光蝕刻法(photolithography)技術使用於此等而形成電路，視需要對電路實施鍍覆，層疊覆蓋膜(cover lay film)，藉此可得到可撓性印刷基板(可撓性配線板)。 A photolithography technique is used to form a circuit, and the circuit is plated as needed, and a cover lay film is laminated to obtain a flexible printed circuit board (flexible wiring board).
因此，本發明之覆銅積層體係將銅箔與樹脂層積層而成。又，本發明之可撓性印刷基板係將電路形成於覆銅積層體之銅箔而成。 Therefore, the copper clad layering system of the present invention is formed by laminating a copper foil and a resin layer. Moreover, the flexible printed circuit board of the present invention is formed by forming a circuit on a copper foil of a copper clad laminate.
作為樹脂層可列舉：PET(聚對酞酸乙二酯)、PI(聚醯亞胺)、LCP(液晶聚合物)、PEN(聚萘二甲酸乙二酯(polyethylene naphthalate))，但並不限定於此等。又，亦可使用此等之樹脂膜作為樹脂層。 Examples of the resin layer include PET (polyethylene terephthalate), PI (polyimine), LCP (liquid crystal polymer), and PEN (polyethylene naphthalate), but they are not Limited to this. Further, a resin film of these may be used as the resin layer.
作為樹脂層與銅箔之積層方法，亦可將成為樹脂層之材料塗布於銅箔的表面，進行加熱成膜。又，亦可使用樹脂膜作為樹脂層，於樹脂膜與銅箔之間使用以下之接著劑，或亦可不使用接著劑，將樹脂膜熱壓接於銅箔。惟，由不將多餘之熱施加於樹脂膜的觀點而言，較佳使用接著劑。 As a method of laminating the resin layer and the copper foil, a material which becomes a resin layer may be applied to the surface of the copper foil, and the film may be formed by heating. Further, a resin film may be used as the 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 an adhesive. However, it is preferable to use an adhesive agent from the viewpoint of not applying excess heat to the resin film.
當使用膜作為樹脂層之情形時，可將此膜經由接著劑層積層於銅箔。於此情形時，較佳使用與膜相同成分之接著劑。例如，當使用聚醯亞胺膜作為樹脂層之情形時，接著劑層較佳亦使用聚醯亞胺系接著劑。另，此處所稱之聚醯亞胺接著劑，係指含有醯亞胺鍵之接著劑，亦包含聚醚醯亞胺等。 When a film is used as the resin layer, the film may be laminated on the copper foil via an adhesive. In this case, it is preferred to use an adhesive of the same composition as the film. For example, when a polyimide film is used as the resin layer, a polyimide layer-based adhesive is preferably used as the adhesive layer. Further, the term "polyimine" as used herein refers to an adhesive containing a quinone bond, and also includes a polyether quinone.
另，本發明並不限定於上述實施形態。又，只要會達成本發明之作用效果，上述實施形態之銅合金亦可含有其他之成分。 Further, the present invention is not limited to the above embodiment. Further, the copper alloy of the above embodiment may contain other components as long as the effects of the present invention are achieved.
例如，亦可對銅箔之表面施以粗化處理、防鏽處理、耐熱處理或此等之組合的表面處理。 For example, the surface of the copper foil may be subjected to a roughening treatment, a rustproof treatment, a heat treatment treatment, or a surface treatment of such a combination.
[實施例] [Examples]
接著，列舉實施例進一步詳細說明本發明，但本發明並不限定於此等。 Next, the present invention will be described in further detail by way of examples, but the invention is not limited thereto.
將表1所示之元素各自添加於純度99.9%以上的電解銅，於Ar環境下進行鑄造，得到鑄錠。鑄錠中之氧含量未達15ppm。以900℃將此鑄錠均質化退火後，進行熱壓延製成厚度30mm後，進行冷壓延至14mm，然後於進行1次退火後，對表面進行端面切削，以表1所示之加工度η進行最後冷壓延而得到最後厚度17μm之箔。對所得到之箔施加300℃×30分之熱處理，得到銅箔樣品。 Each of the elements shown in Table 1 was added to electrolytic copper having a purity of 99.9% or more, and was cast in an Ar atmosphere to obtain an ingot. The oxygen content in the ingot is less than 15 ppm. The ingot was homogenized and annealed at 900 ° C, and then hot rolled to a thickness of 30 mm, and then cold-rolled to 14 mm, and then subjected to one-time annealing to face-cut the surface, and the degree of processing shown in Table 1 was performed. η was subjected to final cold rolling to obtain a foil having a final thickness of 17 μm. A heat treatment of 300 ° C × 30 minutes was applied to the obtained foil to obtain a copper foil sample.
<A.銅箔樣品之評價> <A. Evaluation of copper foil samples>
1.導電率 Conductivity
關於上述熱處理後之各銅箔樣品，依照JIS H 0505藉由4端子法，測量25℃之導電率(%IACS)。 With respect to each copper foil sample after the above heat treatment, the conductivity (% IACS) at 25 ° C was measured by a 4-terminal method in accordance with JIS H 0505.
若導電率在75%IACS以上，則導電性為良好。 When the electrical conductivity is 75% IACS or more, the electrical conductivity is good.
2.粒徑 2. Particle size
使用SEM(Scanning Electron Microscope)觀察上述熱處理後之各銅箔樣品表面，依照JIS H 0501求出平均粒徑。惟，雙晶視為各別之晶粒進行測量。使測量區域為表面之100μm×100μm。 The surface of each of the copper foil samples after the heat treatment was observed by SEM (Scanning Electron Microscope), and the average particle diameter was determined in accordance with JIS H 0501. However, twins are considered as separate crystals for measurement. The measurement area was made 100 μm × 100 μm of the surface.
3.銅箔之彎折性(MIT抗折性) 3. Bending property of copper foil (MIT folding resistance)
關於上述熱處理後之各銅箔樣品，依照JIS P 8115測量MIT抗折次數(來回彎折次數)。其中，使彎折夾R為0.38，負重為500g。 Regarding each of the copper foil samples after the above heat treatment, the MIT bending resistance number (the number of times of bending back and forth) was measured in accordance with JIS P 8115. Among them, the bending clip R was 0.38 and the load was 500 g.
若MIT抗折次數在75次以上，則銅箔之彎折性為良好。 When the MIT bending resistance number is 75 or more, the bending property of the copper foil is good.
4.銅箔之拉伸強度 4. Tensile strength of copper foil
關於上述熱處理後之各銅箔樣品，藉由依據IPC-TM650之拉伸測試，以上述條件測量拉伸強度。 With respect to each of the copper foil samples after the above heat treatment, the tensile strength was measured under the above conditions by a tensile test in accordance with IPC-TM650.
<B.CCL之評價> <B.CCL evaluation>
5.CCL之彎折性 5. CCL bending
於最後冷壓延後對沒有進行上述熱處理之銅箔樣品(熱處理前之銅箔)的單面進行銅粗化鍍覆。使用Cu：10-25g/L、硫酸：20-100g/L之組成作為銅粗化鍍浴，以浴溫20-40℃，電流密度30-70A/dm2進行電鍍1-5秒，使銅附著量為20g/dm2。 After the final cold rolling, copper roughening plating was performed on one side of the copper foil sample (copper foil before heat treatment) which was not subjected to the above heat treatment. Cu: 10-25g / L, sulfuric acid: 20-100g / L composition as a copper roughening bath, bath temperature of 20-40 ° C, current density of 30-70A / dm 2 for 1-5 seconds, copper The amount of adhesion was 20 g/dm 2 .
將聚醯亞胺膜(宇部興產股份有限公司製之製品名「upilex VT」，厚度25μm)積層於銅箔樣品之粗化鍍覆面，以加熱加壓(4MPa)施加300℃×30分之熱處理進行貼合，得到CCL樣品。關於使用於彎折測試之CCL樣品的尺寸，壓延方向(長邊方向)為50mm，寬度方向為12.7mm。 Polyimide film (product name "upilex VT" manufactured by Ube Industries, Ltd., thickness 25 μm) was laminated on the roughened plating surface of the copper foil sample, and applied at 300 ° C × 30 °C under heat and pressure (4 MPa). The heat treatment was carried out to obtain a CCL sample. Regarding the size of the CCL sample used for the bending test, the rolling direction (longitudinal direction) was 50 mm, and the width direction was 12.7 mm.
如圖1所示，以使銅箔面成為外側之方式將此CCL樣品30於長邊方向之中央對折，挾入0.1mm厚之板20(JIS-H3130(C1990)所規定之鈦銅板)，配置於壓縮測試機10(島津製作所公司製造之製品名「Autograph AGS」)之下模具10a與上模具10b之間。 As shown in Fig. 1, the CCL sample 30 was folded in the center in the longitudinal direction so that the copper foil surface was outside, and the 0.1 mm thick plate 20 (titanium copper plate specified in JIS-H3130 (C1990)) was inserted. It is disposed between the mold 10a and the upper mold 10b under the compression tester 10 (product name "Autograph AGS" manufactured by Shimadzu Corporation).
於此狀態下，使上模具10b降下，將CCL樣品30於對折部分彎折成密接於板20(圖1(a))。立即將CCL樣品30自壓縮測試機10取出，使用顯微鏡(其恩斯公司製造之製品名「One Shot 3D測量顯微鏡VR-3000」，以倍率200倍藉由目視確認對折部分「横向V字」狀之彎折前端部30s銅箔面有無裂縫。另，彎折前端部30s相當於彎曲半徑0.05mm之180度密接彎曲。 In this state, the upper mold 10b is lowered, and the CCL sample 30 is bent at the folded portion to be in close contact with the plate 20 (Fig. 1 (a)). Immediately, the CCL sample 30 was taken out from the compression tester 10, and the "Front V-shaped" portion of the folded portion was visually confirmed by a magnification of 200 times using a microscope (the product name "One Shot 3D Measuring Microscope VR-3000" manufactured by Ens Corporation). The bent front end portion 30s has a crack on the copper foil surface. Further, the bent front end portion 30s corresponds to a 180 degree tight bend of a bending radius of 0.05 mm.
當確認到裂縫之情形時，結束測試，使進行圖1(a)之壓縮的次數為CCL的彎折次數。 When the crack is confirmed, the test is terminated so that the number of times of compression performed in Fig. 1(a) is the number of bends of the CCL.
當未確認到裂縫之情形時，如圖1(b)所示，使彎折前端部30s朝上，將CCL樣品30配置於壓縮測試機10之下模具10a與上模具10b之間，於此狀態下使10b降下，將彎折前端部30s打開。 When the crack is not confirmed, as shown in Fig. 1(b), the bent front end portion 30s is directed upward, and the CCL sample 30 is disposed between the lower mold 10a and the upper mold 10b under the compression tester 10, in this state. Lower 10b is lowered to open the bent front end portion 30s.
然後，再次進行圖1(a)之彎折，同樣地藉由目視確認彎折前端部30s有無裂縫。以下，同樣地反覆進行圖1(a)~(b)之步驟，決定彎折次數。 Then, the bending of FIG. 1(a) was performed again, and the presence or absence of cracks in the bent front end portion 30s was visually confirmed in the same manner. Hereinafter, the steps of FIGS. 1(a) to 1(b) are repeated in the same manner, and the number of times of bending is determined.
若CCL之彎折次數在3次以上，則CCL的彎折性為良好。 If the number of bending of the CCL is three or more times, the bending property of the CCL is good.
6.蝕刻性 6. Etchability
將L/S(直線/間隔)=40/40μm、35/35μm、25/25μm、20/20μm及15/15μm之細長狀電路形成在上述CCL樣品的銅箔部分。作為比較，與市售之壓延銅箔(精銅箔)同樣地形成電路。然後，以顯微鏡目視判定蝕刻因子(電路(蝕刻深度/上下之平均蝕刻寬度)所表示之比)及電路之直線性，以下述之基準進行評價。若評價為○，則佳。 An elongated circuit of L/S (straight line/space) = 40/40 μm, 35/35 μm, 25/25 μm, 20/20 μm, and 15/15 μm was formed in the copper foil portion of the above CCL sample. For comparison, a circuit was formed in the same manner as a commercially available rolled copper foil (fine copper foil). Then, the etching factor (the ratio of the circuit (etching depth/average etching width)) and the linearity of the circuit were visually observed by a microscope, and evaluated based on the following criteria. If the evaluation is ○, it is better.
○：相較於市售之壓延銅箔，蝕刻因子及電路的直線性良好 ○: The etch factor and the linearity of the circuit are good compared to the commercially available rolled copper foil.
△：相較於市售之壓延銅箔，蝕刻因子及電路的直線性相同 △: The etch factor and the linearity of the circuit are the same as those of the commercially available rolled copper foil.
×：相較於市售之壓延銅箔，蝕刻因子及電路的直線性差 ×: The etch factor and the linearity of the circuit are poor compared to commercially available rolled copper foil
將所得到之結果示於表1。 The results obtained are shown in Table 1.
[表1]
如從表1可清楚得知，當銅箔之平均結晶粒徑為0.5~4.0μm，且拉伸強度為235~290MPa之各個實施例的情形時，彎折性及蝕刻性優異。 As is clear from Table 1, when the average crystal grain size of the copper foil is 0.5 to 4.0 μm and the tensile strength is 235 to 290 MPa, the bending property and the etching property are excellent.
另一方面，當於最後冷壓延之加工度η未達3.5之比較例1、3、6的情形時，銅箔之平均結晶粒徑超過4.0μm，拉伸強度未達235MPa，銅箔及CCL之彎折性差。另，於比較例6之情形時，銅箔之平均結晶粒徑由於為稍大於4.0μm之4.5μm，故蝕刻性良好。 On the other hand, when the processing degree η of the final cold rolling is less than 3.5, the average crystal grain size of the copper foil exceeds 4.0 μm, the tensile strength is less than 235 MPa, and the copper foil and CCL are used. The bending is poor. Further, in the case of Comparative Example 6, the average crystal grain size of the copper foil was 4.5 μm which was slightly larger than 4.0 μm, so that the etching property was good.
當含有Ag但不含有添加元素之比較例2的情形時，及添加元素之合計含量未達下限值之比較例5的情形時，利用添加元素之再結晶粒的微細化不足，銅箔之平均結晶粒徑大幅超過4.0μm，為粗大化，拉伸強度未達235MPa，則銅箔之彎折性及蝕刻性差。 In the case of Comparative Example 2 containing Ag but not containing an additive element, and in the case of Comparative Example 5 in which the total content of the additive elements did not reach the lower limit value, the refinement of the recrystallized grains by the additive element was insufficient, and the copper foil was When the average crystal grain size greatly exceeds 4.0 μm and is coarsened, and the tensile strength is less than 235 MPa, the copper foil is inferior in bending property and etching property.
當添加元素之合計含量超過上限值之比較例4的情形時，導電率差。 When the total content of the added elements exceeds the upper limit value, the conductivity is inferior.
當Ag含量超過0.05質量%之比較例7的情形時，再結晶溫度變高，於300℃之熱處理，不會再結晶，導電率下降，且拉伸強度變高超過290MPa。因此，銅箔及CCL之彎折性大幅地劣化。 When the Ag content exceeds 0.05% by mass in the case of Comparative Example 7, the recrystallization temperature becomes high, and heat treatment at 300 ° C does not recrystallize, the electrical conductivity decreases, and the tensile strength becomes higher than 290 MPa. Therefore, the bending property of the copper foil and the CCL is largely deteriorated.
10‧‧‧壓縮測試機 10‧‧‧Compression test machine
10a‧‧‧下模具 10a‧‧‧Mold
10b‧‧‧上模具 10b‧‧‧Upper mold
20‧‧‧板 20‧‧‧ board
30‧‧‧CCL樣品 30‧‧‧CCL samples
30s‧‧‧彎折前端部 30s‧‧‧Bent front end
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP2016-020759 | 2016-02-05 | ||
| JP2016020759 | 2016-02-05 | ||
| JPJP2016-063233 | 2016-03-28 | ||
| JP2016063233A JP6392268B2 (en) | 2016-02-05 | 2016-03-28 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201734219A true TW201734219A (en) | 2017-10-01 |
| TWI646207B TWI646207B (en) | 2019-01-01 |
Family
ID=59628683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW105143778A TWI646207B (en) | 2016-02-05 | 2016-12-29 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6392268B2 (en) |
| KR (1) | KR101935128B1 (en) |
| TW (1) | TWI646207B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113125280A (en) * | 2021-03-29 | 2021-07-16 | 合肥奕斯伟材料技术有限公司 | Calculation method for bending resistance test of COF Film finished product |
| CN115179638A (en) * | 2022-06-29 | 2022-10-14 | 厦门爱谱生电子科技有限公司 | Manufacturing method of flexible copper-clad plate |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6712561B2 (en) * | 2017-03-21 | 2020-06-24 | Ｊｘ金属株式会社 | Rolled copper foil for flexible printed circuit board, copper clad laminate using the same, flexible printed circuit board, and electronic device |
| JP6793138B2 (en) * | 2018-01-22 | 2020-12-02 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit boards, copper-clad laminates using it, flexible printed circuit boards, and electronic devices |
| JP6926013B2 (en) * | 2018-02-23 | 2021-08-25 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit, products for sale of copper foil for flexible printed circuit, copper-clad laminate using it, flexible printed circuit, and electronic equipment |
| JP2019194360A (en) * | 2019-06-26 | 2019-11-07 | Ｊｘ金属株式会社 | Copper foil for flexible printed wiring board, and copper clad laminate, flexible printed wiring board and electronic device using the same |
| JP7014211B2 (en) * | 2019-09-27 | 2022-02-01 | 三菱マテリアル株式会社 | Copper alloys for electronic / electrical equipment, copper alloy strips for electronic / electrical equipment, parts for electronic / electrical equipment, terminals, and bus bars |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5235080B2 (en) * | 2007-09-28 | 2013-07-10 | Ｊｘ日鉱日石金属株式会社 | Copper alloy foil and flexible printed circuit board using 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 |
| JP5588607B2 (en) * | 2007-10-31 | 2014-09-10 | 三井金属鉱業株式会社 | Electrolytic copper foil and method for producing the electrolytic copper foil |
| JP5285578B2 (en) * | 2009-11-13 | 2013-09-11 | 株式会社カネカ | Insulating polyimide film, coverlay film and flexible printed wiring board |
| JP5826160B2 (en) * | 2012-04-10 | 2015-12-02 | Jx日鉱日石金属株式会社 | Rolled copper foil, copper-clad laminate, flexible printed wiring board and manufacturing method thereof |
| JP6104200B2 (en) * | 2014-03-13 | 2017-03-29 | Ｊｘ金属株式会社 | Rolled copper foil, copper clad laminate, flexible printed circuit board, and electronic device |
-
2016
- 2016-03-28 JP JP2016063233A patent/JP6392268B2/en active Active
- 2016-12-29 TW TW105143778A patent/TWI646207B/en active
-
2017
- 2017-01-23 KR KR1020170010379A patent/KR101935128B1/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113125280A (en) * | 2021-03-29 | 2021-07-16 | 合肥奕斯伟材料技术有限公司 | Calculation method for bending resistance test of COF Film finished product |
| CN113125280B (en) * | 2021-03-29 | 2024-01-02 | 合肥颀材科技有限公司 | Calculation method for bending resistance test of finished product COF Film |
| CN115179638A (en) * | 2022-06-29 | 2022-10-14 | 厦门爱谱生电子科技有限公司 | Manufacturing method of flexible copper-clad plate |
| CN115179638B (en) * | 2022-06-29 | 2024-02-27 | 厦门爱谱生电子科技有限公司 | Manufacturing method of flexible copper-clad plate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170093706A (en) | 2017-08-16 |
| JP2017143233A (en) | 2017-08-17 |
| JP6392268B2 (en) | 2018-09-19 |
| TWI646207B (en) | 2019-01-01 |
| KR101935128B1 (en) | 2019-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI646207B (en) | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device | |
| KR101935129B1 (en) | Copper foil for flexible printed wiring board, and copper-clad laminate, flexible printed wiring board and electronic device using the same | |
| TWI588273B (en) | Copper alloy foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board and electronic equipment | |
| KR102098479B1 (en) | Copper foil for flexible printed circuit, copper clad laminate using the same, flexible printed circuit and electronic device | |
| JP6781562B2 (en) | Copper foil for flexible printed circuit boards, copper-clad laminates using it, flexible printed circuit boards, and electronic devices | |
| KR102470725B1 (en) | Copper foil for flexible printed circuit, and copper clad laminate, flexible printed circuit and electronic device using copper foil | |
| CN107046763B (en) | Copper foil for flexible printed board and copper-clad laminate using same | |
| KR20170113104A (en) | Copper foil for flexible printed wiring board, copper-clad laminate using the same, flexible printed wiring board and electronic device | |
| JP5694094B2 (en) | Copper foil for flexible printed wiring board, copper-clad laminate, flexible printed wiring board, and electronic device | |
| JP6348621B1 (en) | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device | |
| CN107046768B (en) | Copper foil for flexible printed board, copper-clad laminate using same, flexible printed board, and electronic device | |
| JP5933943B2 (en) | Rolled copper foil for flexible printed wiring boards, copper-clad laminates, flexible printed wiring boards, and electronic equipment | |
| JP4430020B2 (en) | Copper foil for flexible printed wiring board, manufacturing method thereof and flexible printed wiring board | |
| TWI718025B (en) | Copper foil for flexible printed circuit boards, copper-clad laminates, flexible printed circuit boards and electronic devices using the same | |
| JP6647253B2 (en) | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device | |
| JP6712561B2 (en) | Rolled copper foil for flexible printed circuit board, copper clad laminate using the same, flexible printed circuit board, and electronic device | |
| JP6030325B2 (en) | Rolled copper foil, copper-clad laminate, flexible printed wiring board, and electronic equipment |