WO2010116976A1 - 2層銅張積層板及びその製造方法 - Google Patents
2層銅張積層板及びその製造方法 Download PDFInfo
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- WO2010116976A1 WO2010116976A1 PCT/JP2010/056179 JP2010056179W WO2010116976A1 WO 2010116976 A1 WO2010116976 A1 WO 2010116976A1 JP 2010056179 W JP2010056179 W JP 2010056179W WO 2010116976 A1 WO2010116976 A1 WO 2010116976A1
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- copper
- layer
- clad laminate
- warpage
- amount
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- 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
- B32B15/088—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 comprising polyamides
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
- H05K2203/0271—Mechanical force other than pressure, e.g. shearing or pulling
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/15—Position of the PCB during processing
- H05K2203/1545—Continuous processing, i.e. involving rolls moving a band-like or solid carrier along a continuous production path
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
Definitions
- the present invention relates to a two-layer copper-clad laminate in which a copper layer is formed on a polyimide film by using a plating process, thereby reducing the amount of warpage of the laminate and reducing the dimensional change rate.
- a two-layer copper clad laminate (CCL) material in which a copper layer is formed on a polyimide film has been used as a circuit material for mounting driver ICs such as liquid crystal displays that require fine pitch circuits.
- a two-layer CCL material used as a laminate material for COF (Chip On Film) a two-layer CCL material produced by using sputtering and plating processes has attracted attention.
- the two-layer CCL material is obtained by forming a submicron copper layer on a polyimide film (PI) by sputtering and then forming a copper layer by copper sulfate plating.
- PI polyimide film
- the laminated material is warped due to moisture absorption of the PI layer and internal stress of the copper layer.
- the warping of the laminated material becomes an obstacle when the CCL material is processed into a COF and when the COF is mounted on a substrate or the like.
- the amount of warping of the laminated material in the COF is a particularly important problem because it causes a collision of a chip or a liquid crystal panel when transported when mounted on a substrate.
- a technique for a PI layer such as a two-layer CCL material that does not cause curling even when the thickness of a BPDA-PPD-based polyimide film is reduced is disclosed (see Patent Document 2).
- the thin film formed on the surface of the support from the BPDA-PPD polymer solution is dried in two specific stages to improve the linear expansion coefficient and thermal dimensional stability, and the copper thin film is bonded.
- a technique for reducing the curl at the time is disclosed (see Patent Document 3).
- the former does not cause curling even if the thickness of the PI layer is reduced by selecting an optimal constituent material as the PI layer, but the same effect is not necessarily obtained depending on the copper lamination method. Is not limited.
- the latter controls the ratio of linear expansion coefficient by carrying out a specific two-stage drying, but how much the amount of substantial warpage is improved only by confirming the appearance of the film. Is unknown.
- the present invention provides a two-layer CCL material in which a copper layer is formed by plating on a polyimide film, and a two-layer CCL material in which the amount of warpage and a dimensional change rate of the laminated material is reduced and a method for manufacturing the two-layer CCL material.
- this application 1) In a two-layer copper-clad laminate in which a copper layer is formed on a polyimide film using a plating process, the copper-clad laminate exhibits a shrinking behavior in the longitudinal (MD) direction, and the amount of warpage of the laminate is 0 to A two-layer copper-clad laminate having a standard deviation of 3.0 mm or less at 10 mm, where the amount of warpage is 100 mm after conditioning at 23 ° C., humidity 50%, 72 hours. The average value of the amount of lifting of the four corners of the two-layer copper-clad laminate is shown.
- the dimension after etching the copper-clad laminate is 0% to 0.030 as compared to the 100 mm square two-layer copper-clad laminate.
- % Copper-clad laminate as described in 1) above which exhibits a behavior of shrinking in a range of%.
- the dimension after etching the copper-clad laminate and further heat-treating is 0% compared to the 100 mm square two-layer copper-clad laminate.
- the two-layer copper-clad laminate according to 1) which exhibits a behavior of shrinking in a range of up to 0.075%
- 4) The two-layer copper-clad laminate as described in any one of 1) to 3) above, wherein the polyimide film has a thickness of 25 to 50 ⁇ m and the copper layer has a thickness of 1 to 20 ⁇ m.
- the electrolytic solution temperature during plating is 55 ° C or higher and 65 ° C or lower, and the line tension is less than 40 kg.
- a method for producing a two-layer copper-clad laminate, in which a copper layer is formed using a plating process characterized by:
- the two-layer copper-clad laminate of the present invention reduces the amount of warpage of the laminate and its variation while maintaining a low dimensional change rate of the laminate in shrinkage in the longitudinal (MD) direction of the copper-clad laminate. Can do. As a result, it is possible to obtain an excellent effect that it is possible to reduce obstacles when processing the CCL material into COF and mounting the COF on a substrate or the like.
- the polyimide film used for the two-layer CCL material of the present invention is not particularly limited as long as the present invention can be achieved, but a BPDA-PPD based polyimide film is preferably used.
- the amount of warping is defined as the average value of the amount of lift of four corners of a 100 mm square sheet after conditioning at a temperature of 23 ° C., a humidity of 50%, and 72 hours. Accordingly, a positive amount of warping means a concave shape with the copper layer surface facing upward, and a negative amount of warping means a convex shape with the copper layer surface facing upward.
- a two-layer copper-clad laminate in which a copper layer is formed on a polyimide film using a plating process, it should be noted that the amount of warpage becomes too large.
- a large amount of warpage means that the two-layer copper clad laminate is deformed, which may be an obstacle in the manufacturing process of a liquid crystal display or the like that requires a fine pitch circuit.
- the electrolyte temperature during plating In order to reduce the amount of warpage, it is effective to control the electrolyte temperature during plating within an appropriate range. Specifically, it is desirable that the electrolyte temperature during plating be 55 ° C. or more and 65 ° C. or less. Furthermore, the amount of warpage can be reduced by increasing the line tension in the manufacturing process. However, if the line tension is excessively increased, the warping is reversed and the manufacturing stability is lost. In addition, the dimensional change (shrinkage) in the longitudinal direction becomes remarkable. Therefore, an adjusted moderate tension is necessary.
- the behavior of shrinking in the longitudinal (MD) direction of the copper-clad laminate (dimensional change)
- the line tension within an appropriate range, the amount of warpage is the same direction and as small as possible, and the dimensional change rate (%) due to the contraction in the longitudinal (MD) direction of the copper-clad laminate is allowed.
- the dimension after etching the copper clad laminate is in the range of 0% to 0.030%, and the dimension after the heat treatment is in the range of 0% to 0.075%.
- the appropriate line tension for keeping such a range that is, the line tension for setting the warping amount to 0 mm to 10 mm is less than 40 kg, and the dimensional change rate (%) is within the proper range.
- the line tension be less than 38 kg, further 35 kg or less. It will be easily understood that the present invention can be used even if it slightly deviates from the range of the line tension depending on the application.
- MD is the dimensional change rate (% change in machine direction) in the longitudinal direction.
- TD is the rate of dimensional change in the transverse direction (% change in transverse direction).
- the dimensional stability of the present invention is based on MD conforming to IPC-TM-650, 2.2.4, Method B and C. Stipulated. In the index of dimensional change rate, shrinkage is expressed as a negative value, and extension as a positive value.
- IPC-TM-650, 2.2.4, Method B is the difference in dimensional change between the copper-clad state and copper-etched state.
- IPC-TM-650, 2.2.4, Method C This is a difference in dimensional change in a state where copper is further etched after being etched.
- the liquid composition and management conditions of the copper layer etchant are as follows.
- (Liquid composition) Cupric chloride solution (CuCl 2 ), copper oxide (CuO)
- Example 1 is a case where the electrolytic solution temperature is 65 ° C. The amount of warpage is 4.21 mm, its standard deviation is 1.45 mm, the dimensional change rate after removing the copper layer is -0.002% in the longitudinal (MD) direction, and the dimensional change rate after removing the copper layer and heating is long. It was -0.061% in the (MD) direction. These conditions all fall within the scope of the present invention, and a suitable two-layer copper-clad laminate was obtained.
- Example 2 is a case where the electrolyte temperature was set to 60 ° C.
- the warpage amount is 6.87 mm
- its standard deviation is 1.52 mm
- the dimensional change rate after removing the copper layer is -0.003% in the longitudinal (MD) direction
- the dimensional change rate after removing the copper layer and heating is long. It was -0.024% in the (MD) direction.
- Example 3 is a case where the electrolyte temperature was 55 ° C.
- the warpage amount is 6.87 mm, its standard deviation is 1.52 mm, the dimensional change rate after removing the copper layer is -0.003% in the longitudinal (MD) direction, and the dimensional change rate after removing the copper layer and heating is long. It was -0.024% in the (MD) direction.
- the comparative example 1 is a case where electrolyte solution temperature is 55 degreeC.
- the dimensional change rate after removing the copper layer is -0.008% in the longitudinal (MD) direction, and the dimensional change rate after removing the copper layer and after heating is -0.038% in the longitudinal (MD) direction, which is particularly problematic. It was not a thing.
- the amount of warpage was as large as 15.68 mm, the standard deviation was 10.31 mm, and the amount of warpage targeted by the present invention exceeded 10 mm, which was an undesirable result.
- Comparative Example 2 The comparative example 2 is a case where electrolyte solution temperature is 46 degreeC.
- the dimensional change after removal of the copper layer is -0.004% in the longitudinal (MD) direction, and the dimensional change after removal of the copper layer and heating is -0.028% in the longitudinal (MD) direction, which is particularly problematic. It was not a thing.
- the amount of warpage was as large as 15.32 mm, and the amount of warpage targeted by the present invention exceeded 10 mm, which was an undesirable result.
- N 18, as in Comparative Example 1.
- a copper layer was formed by plating on a polyimide film (Kapton-ENC, manufactured by Toray DuPont Co., Ltd.). Specifically, it was formed using the drum type electroplating apparatus shown in FIG. The electrolytic solution temperature during plating is kept constant at 60 ° C., the line tension is changed to 28 kg, 35 kg, 38 kg, 40 kg, 43 kg, and 50 kg, and the warpage amount and the dimensional change rate are shown in Table 2. The line tension was the total of the line tension at UW and the line tension at # 1 in FIG.
- Example 4 As shown in Table 2, Example 4 is a case where the line tension is 28 kg. The warpage amount was 7.00 mm, the dimensional change rate after removal of the copper layer was ⁇ 0.021% in the longitudinal (MD) direction, and the dimensional change rate after removal of the copper layer and heating was ⁇ 0.0. 057%. These conditions all fall within the scope of the present invention, and a suitable two-layer copper-clad laminate was obtained.
- Example 5 As shown in Table 2, Example 5 is a case where the line tension is 35 kg. The warpage amount was 6.28 mm, the dimensional change rate after removal of the copper layer was ⁇ 0.028% in the longitudinal (MD) direction, and the dimensional change rate after removal of the copper layer and heating was ⁇ 0. 072%. These conditions all fall within the scope of the present invention, and a suitable two-layer copper-clad laminate was obtained.
- Example 6 As shown in Table 2, Example 6 is a case where the line tension is 38 kg.
- the warpage amount was 5.22 mm
- the dimensional change rate after removal of the copper layer was ⁇ 0.033% in the longitudinal (MD) direction
- the dimensional change rate after removal of the copper layer and heating was ⁇ 0.03 mm in the longitudinal (MD) direction. 088%.
- the dimensional change rate after heating became slightly large as -0.088% in the longitudinal (MD) direction, but the amount of warpage was small and it can be used according to the application.
- the line tension is increased, the dimensional change rate after heating tends to increase in the longitudinal (MD) direction.
- the line tension is less than 40 kg, an increase in the dimensional change rate can be allowed depending on the application.
- Comparative Example 3 is a case where the line tension is 40 kg.
- the warpage amount was 4.81 mm
- the dimensional change rate after removal of the copper layer was ⁇ 0.049% in the longitudinal (MD) direction
- the dimensional change rate after removal of the copper layer and heating was ⁇ 0. 100%.
- the size after etching the copper clad laminate is 0.049%
- the size after heat treatment is 0.1%. There wasn't.
- Comparative Example 4 is a case where the line tension is 43 kg.
- the warpage amount was -1.96 mm
- the dimensional change rate after removing the copper layer was -0.059% in the longitudinal (MD) direction
- the dimensional change rate after removing the copper layer and heating was longitudinal (MD ) Direction was -0.118%. It could not be said to be a suitable two-layer copper clad laminate having large shrinkage.
- the target warpage amount in the present invention was 0 ⁇ m or more
- the warpage of Comparative Example 4 was a negative value, that is, a convex shape with the copper layer surface facing upward, which was not preferable.
- Comparative Example 5 is a case where the line tension is 50 kg.
- the warpage amount was -19.81 mm
- the dimensional change rate after removing the copper layer was -0.078% in the longitudinal (MD) direction
- the dimensional change rate after removing the copper layer and heating was longitudinal (MD ) Direction was -0.140%. It could not be said to be a suitable two-layer copper clad laminate having large shrinkage.
- the target warpage amount in the present invention is 0 ⁇ m or more
- the warpage of Comparative Example 5 is a negative value, that is, a large convex shape with the copper layer surface facing upward, which is a very unfavorable state. It was.
- the line tension is less than 40 kg, the amount of warping is positive, but when the line tension is 40 kg or more, the amount of warping becomes negative and the behavior of warping becomes unstable.
- the dimensional change rate (B method and C method) was found that MD approached 0% as the line tension decreased.
- the line tension is preferably less than 40 kg, and if it is less than 38 kg, MD contracts by 0% to 0.03% in the method B, and contracts by 0% to 0.075% in the method C. So it is a recommended condition.
- the two-layer copper-clad laminate of the present invention has a reduced amount of warpage and its variation, and the amount of change between the dimensions when forming the copper layer and the dimensions after removing the copper layer (Method B), and the copper layer
- the amount of change (Method C) between the dimension during formation and the dimension after PI heating is reduced (the absolute value of the dimensional change rate is reduced).
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Abstract
Description
2層CCL材はポリイミドフィルム(PI)上に、スパッタリングによりサブミクロン程度の銅層を形成した後、硫酸銅メッキ処理により銅層を形成したものである。基本発明は、下記特許文献1に記載されている。
また、BPDA-PPD系のポリマー溶液から支持体表面に形成された薄膜を特定の二段階の乾燥を行うことにより、線膨張係数及び熱寸法安定性を良好なものとし、銅薄を貼り合わせた際のカールを低減する技術が開示されている(特許文献3参照)。
しかし、前者は、PI層として最適な構成材料を選択することによって、PI層の厚みを小さくしてもカールを生じさせないものであるが、銅の積層方法によっては必ずしも同様の効果が得られるとは限らない。また後者は、特定の二段階の乾燥を行うことにより、線膨張係数の比を制御しているが、フィルムの状態を外観上確認するのみで、実質的な反り量についてどの程度改善されているかは不明である。
1)ポリイミドフィルム上にメッキ処理を用いて銅層を形成した2層銅張積層板において、銅張積層板の長手(MD)方向で収縮する挙動を示し、当該積層材の反り量が0~10mmであって、標準偏差が3.0mm以下であることを特徴とする2層銅張積層板、但し、反り量は、23°C、湿度50%、72時間、調湿した後の、100mm角の2層銅張積層板の4角の浮き上がり量の平均値を示す、
2)銅張積層板の長手(MD)方向の寸法変化挙動において、100mm角の2層銅張積層板と対比して、該銅張積層板をエッチングした後の寸法が0%~0.030%の範囲で収縮する挙動を示すことを特徴とする上記1)記載の2層銅張積層板、
3)銅張積層板の長手(MD)方向の寸法変化挙動において、100mm角の2層銅張積層板と対比して、該銅張積層板をエッチングし、さらに熱処理した後の寸法が0%~0.075%の範囲で収縮する挙動を示すことを特徴とする上記1)記載の2層銅張積層板、
4)ポリイミドフィルムの厚さが25~50μm、銅層の厚さが1~20μmであることを特徴とする上記1)~3)のいずれかに記載の2層銅張積層板、
5)ポリイミドフィルム上にメッキ処理を用いて銅層を形成する2層銅張積層板の製造方法において、メッキ時の電解液温度を55°C以上、65°C以下とし、ライン張力を40kg未満とすることを特徴とするメッキ処理を用いて銅層を形成する2層銅張積層板の製造方法、を提供する。
本発明において反り量は、温度23°C、湿度50%、72時間調湿後の100mm角シートの4角の浮き上がり量の平均値と定義する。したがって、反り量がプラスとは、銅層表面を上に向けた状態で凹形状をとり、反り量がマイナスとは、銅層表面を上に向けた状態で凸形状をとることを意味する。
さらには、製作工程においてライン張力を大きくかけることで反り量を低減させることができる。しかしながら、ライン張力を大きくしすぎると、反りが逆方向になり、製造上の安定性を欠く状態となってしまう。また、長手方向の寸法変化(収縮)についても顕著となる。したがって、調整された適度な張力が必要である。
したがって、ライン張力を適正な範囲でかけることにより、反り量が同一方向であり、かつできるだけ小さくすると共に、許容される銅張積層板の長手(MD)方向の収縮による寸法変化率(%)において、銅張積層板をエッチングした後の寸法を0%~0.030%の範囲とし、熱処理した後の寸法を0%~0.075%の範囲とするのが望ましい。
なお、用途に応じては、上記ライン張力の範囲から多少逸脱する場合があっても、使用できることは容易に理解されるであろう。
IPC-TM-650, 2.2.4, Method Bは、銅張り状態と銅をエッチングした状態での寸法変化の差であり、IPC-TM-650, 2.2.4, Method Cは、銅張り状態と銅をエッチングした後に、さらに加熱処理した状態での寸法変化の差である。
(液組成)
塩化第二銅溶液(CuCl2)、酸化銅(CuO)
塩酸(HCl):3.50mol/L(0~6mol/Lの範囲で調整)
過酸化水素(H2O2):30.0Cap(0~99.9Capの範囲で調整)
比重:1.26(1.100~1.400の範囲で調整)
(液温):50°C(45~55°Cの範囲で調整)
・加熱処理の条件は、次の通りである。
IPC-TM-650, 2.2.4, Method Cに準拠した条件(150°C±2°C、30分±2分)
ポリイミドフィルム(東レ・デュポン株式会社製,Kapton-ENC)の上にメッキ処理を施して銅層を形成した。具体的には、図1に示されるドラム式電気メッキ装置を用いて形成した。メッキ時の銅箔にかかるライン張力を一定にし、電解液温度を65°C、60°C、55°C、53°C、46°Cと変更し、それぞれにおける反り量及び寸法変化率を表1に示す。なお、実施例1及び実施例2に使用したロット数(テストに使用した個数)はN=6である。
実施例1は、電解液温度を65°Cとした場合である。反り量が4.21mm、その標準偏差が1.45mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.002%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.061%となった。これらの条件は、いずれも本願発明の範囲に入るものであり、好適な2層銅張積層板が得られた。
実施例2は、電解液温度を60°Cとした場合である。反り量が6.87mm、その標準偏差が1.52mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.003%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.024%となった。これらの条件は、いずれも本願発明の範囲に入るものであり、好適な2層銅張積層板が得られた。
実施例2は、電解液温度を55°Cとした場合である。反り量が6.87mm、その標準偏差が1.52mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.003%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.024%となった。これらの条件は、いずれも本願発明の範囲に入るものであり、好適な2層銅張積層板が得られた。
比較例1は、電解液温度を55°Cとした場合である。銅層除去後の寸法変化率が長手(MD)方向で-0.008%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.038%となり、特に問題となるものではなかった。しかし、この比較例1では、反り量が15.68mmと大きく、その標準偏差が10.31mmとなり、本願発明で目標とする反り量が10mmを超え、好ましくない結果となった。なお、この比較例1に使用したロット数(テストに使用した個数)はN=18である。
比較例2は、電解液温度を46°Cとした場合である。銅層除去後の寸法変化率が長手(MD)方向で-0.004%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.028%となり、特に問題となるものではなかった。しかし、この比較例2では、反り量が15.32mmと大きくなり、本願発明で目標とする反り量が10mmを超え、好ましくない結果となった。なお、この比較例2に使用したロット数(テストに使用した個数)は、比較例1と同様に、N=18である。
ポリイミドフィルム(東レ・デュポン株式会社製,Kapton-ENC)の上にメッキ処理を施して銅層を形成した。具体的には、図1に示されるドラム式電気メッキ装置を用いて形成した。メッキ時の電解液温度を60°Cと一定にし、ライン張力を28kg、35kg、38kg、40kg、43kg、50kgと変更し、それぞれにおける反り量及び寸法変化率を表2に示す。
なお、上記ライン張力は、図1における、UWでのライン張力と#1でのライン張力との合計値とした。
表2に示すように、実施例4は、ライン張力を28kgとした場合である。反り量が7.00mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.021%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.057%となった。これらの条件は、いずれも本願発明の範囲に入るものであり、好適な2層銅張積層板が得られた。
表2に示すように、実施例5は、ライン張力を35kgとした場合である。反り量が6.28mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.028%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.072%となった。これらの条件は、いずれも本願発明の範囲に入るものであり、好適な2層銅張積層板が得られた。
表2に示すように、実施例6は、ライン張力を38kgとした場合である。反り量が5.22mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.033%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.088%となった。この結果、加熱後の寸法変化率が長手(MD)方向で-0.088%とやや大きくなったが、反り量が少なく、用途に応じて使用できるものである。
ライン張力を増加させると加熱後の寸法変化率が長手(MD)方向で大きくなる傾向を示すが、ライン張力が40kg未満であれば、寸法変化率の増加を用途によっては許容できるものである。
表2に示すように、比較例3は、ライン張力を40kgとした場合である。反り量が4.81mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.049%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.100%となった。
反りの発生は小さいが、銅張積層板をエッチングした後の寸法が0.049%、熱処理した後の寸法が0.1%となって収縮が大きく好適な2層銅張積層板とは言えなかった。
表2に示すように、比較例4は、ライン張力を43kgとした場合である。比較例4では、反り量が-1.96mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.059%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.118%となった。収縮が大きく好適な2層銅張積層板とは言えなかった。
また、本願発明で目標とする反り量が0μm以上に対して、比較例4の反りは、マイナスの値、すなわち銅層表面を上に向けた状態で凸形状となり、好ましくない状態であった。
表2に示すように、比較例5は、ライン張力を50kgとした場合である。比較例5では、反り量が-19.81mmとなり、銅層除去後の寸法変化率が長手(MD)方向で-0.078%となり、銅層除去さらに加熱後の寸法変化率が長手(MD)方向で-0.140%となった。収縮が大きく好適な2層銅張積層板とは言えなかった。
また、本願発明で目標とする反り量が0μm以上に対して、比較例5の反りは、マイナスの値、すなわち銅層表面を上に向けた状態で大きな凸形状となり、極めて好ましくない状態であった。
特に、ライン張力が40kg未満であることが好ましく、さらに38kg未満であれば、MDは、B法では0%~0.03%の収縮、C法では0%~0.075%の収縮となるので推奨される条件である。
Claims (5)
- ポリイミドフィルム上にメッキ処理を用いて銅層を形成した2層銅張積層板において、銅張積層板の長手(MD)方向で収縮する挙動を示し、当該積層材の反り量が0~10mmであって、標準偏差が3.0mm以下であることを特徴とする2層銅張積層板、但し、反り量は、23°C、湿度50%、72時間、調湿した後の、100mm角の2層銅張積層板の4角の浮き上がり量の平均値を示す、
- 銅張積層板の長手(MD)方向の寸法変化挙動において、100mm角の2層銅張積層板と対比して、該銅張積層板をエッチングした後の寸法が0%~0.030%の範囲で収縮する挙動を示すことを特徴とする請求項1記載の2層銅張積層板、
- 銅張積層板の長手(MD)方向の寸法変化挙動において、100mm角の2層銅張積層板と対比して、該銅張積層板をエッチングし、さらに熱処理した後の寸法が0%~0.075%の範囲で収縮する挙動を示すことを特徴とする請求項1記載の2層銅張積層板、
- ポリイミドフィルムの厚さが25~50μm、銅層の厚さが1~20μmであることを特徴とする請求項1~3のいずれか一項に記載の2層銅張積層板、
- ポリイミドフィルム上にメッキ処理を用いて銅層を形成する2層銅張積層板の製造方法において、メッキ時の電解液温度を55°C以上、65°C以下とし、ライン張力を38kg未満とすることを特徴とするメッキ処理を用いて銅層を形成する2層銅張積層板の製造方法。
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JP2016066647A (ja) * | 2014-09-22 | 2016-04-28 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法 |
JP2016064516A (ja) * | 2014-09-22 | 2016-04-28 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法 |
JP2016087898A (ja) * | 2014-10-31 | 2016-05-23 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法、並びにそれを用いたフレキシブル配線板及びその製造方法 |
JP2016087899A (ja) * | 2014-10-31 | 2016-05-23 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法、並びにそれを用いたフレキシブル配線板及びその製造方法 |
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JP2006306009A (ja) * | 2004-07-27 | 2006-11-09 | Kakogawa Plastic Kk | 2層フィルム、2層フィルムの製造方法およびプリント基板の製造方法 |
JP3912611B2 (ja) * | 2005-04-18 | 2007-05-09 | 東洋紡績株式会社 | 金属化ポリイミドフィルム、金属化ポリイミドフィルムロールおよびフレキシブルプリント配線板 |
JP2007168370A (ja) * | 2005-12-26 | 2007-07-05 | Du Pont Toray Co Ltd | 銅張り板 |
JP4158942B2 (ja) * | 2006-10-03 | 2008-10-01 | 古河電気工業株式会社 | 金属張積層体の製造方法 |
JP2008137178A (ja) * | 2006-11-30 | 2008-06-19 | Toray Ind Inc | 金属層付きフィルム、これを用いたフレキシブル回路基板および半導体装置 |
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WO2006109753A1 (ja) * | 2005-04-07 | 2006-10-19 | Ube Industries, Ltd. | ポリイミドフィルムの製造方法およびポリイミドフィルム |
WO2008065890A1 (fr) * | 2006-11-29 | 2008-06-05 | Nippon Mining & Metals Co., Ltd. | Stratifié bicouches à placage de cuivre |
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JP2016066647A (ja) * | 2014-09-22 | 2016-04-28 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法 |
JP2016064516A (ja) * | 2014-09-22 | 2016-04-28 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法 |
JP2016087898A (ja) * | 2014-10-31 | 2016-05-23 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法、並びにそれを用いたフレキシブル配線板及びその製造方法 |
JP2016087899A (ja) * | 2014-10-31 | 2016-05-23 | 住友金属鉱山株式会社 | 2層銅張積層板及びその製造方法、並びにそれを用いたフレキシブル配線板及びその製造方法 |
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