JP2016121394A - Electrolytic copper foil, and fccl and ccl including the same - Google Patents
Electrolytic copper foil, and fccl and ccl including the same Download PDFInfo
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- copper foil
- electrolytic copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000011889 copper foil Substances 0.000 title claims abstract description 108
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 34
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000011241 protective layer Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000000788 chromium alloy Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 10
- 230000037303 wrinkles Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 238000005498 polishing Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWNCIXFIIDVRKE-UHFFFAOYSA-N 3-methyl-2-(4-methylphenyl)morpholine Chemical compound CC1NCCOC1C1=CC=C(C)C=C1 NWNCIXFIIDVRKE-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- 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
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
Abstract
Description
本発明は、電解銅箔、これを含むＦＣＣＬ及びＣＣＬに関し、より詳しくは、一面の表面因子であるＳＣ（３次元的に測定された一面の実表面積を、該面の平面視面積（測定単位面積）で割った値）の調節によって工程性が向上した電解銅箔、これを含むＦＣＣＬ及びＣＣＬに関する。 The present invention relates to an electrolytic copper foil, and FCCL and CCL including the electrolytic copper foil. More specifically, the surface factor of one surface is SC (the actual surface area of one surface measured three-dimensionally, the planar view area of the surface (measurement unit). The present invention relates to an electrolytic copper foil whose processability is improved by adjusting the value divided by area), FCCL and CCL including the same.
印刷回路基板（ＰＣＢ； Ｐｒｉｎｔｅｄ ｃｉｒｃｕｉｔ ｂｏａｒｄ）は、各種部品を接続する電気配線を回路設計に従って配線図形で表したものであって、各種部品を連結または支持する役割をする。特に、ノートブックコンピュータ、携帯電話、ＰＤＡ、小型ビデオカメラ及び電子手帳などの電子機器の発達につれ印刷回路基板の需要が増大した。更に、前記電子機器の携帯性が強調されることによって次第に小型化及び軽量化していく傾向にある。したがって、印刷回路基板は、さらに集積化、小型化及び軽量化している。 A printed circuit board (PCB) represents electrical wiring for connecting various components in a wiring pattern according to a circuit design, and serves to connect or support the various components. In particular, the demand for printed circuit boards has increased with the development of electronic devices such as notebook computers, mobile phones, PDAs, small video cameras, and electronic notebooks. Furthermore, the emphasis is placed on the portability of the electronic device, and there is a tendency to gradually reduce the size and weight. Therefore, the printed circuit board is further integrated, reduced in size and reduced in weight.
前記印刷回路基板は、その物理的特性に従ってリジッド（ｒｉｇｉｄ）印刷回路基板、軟性（ｆｌｅｘｉｂｌｅ）印刷回路基板、その二つが結合したリジッド−フレキシブル印刷回路基板及びリジッド−フレキシブル印刷回路基板に類似なマルチ−フレキシブル印刷回路基板に分けられる。特に、軟性印刷回路基板の原資材である軟性銅張箔積層板（ＦＣＣＬ； Ｆｌｅｘｉｂｌｅ Ｃｏｐｐｅｒ Ｃｌａｄ Ｌａｍｉｎａｔｅ）は、携帯電話、デジタルカムコーダー、ノートブックコンピュータ、ＬＣＤモニターなど、デジタル家電製品に使われるものであって、屈曲性が大きくて軽薄短小化に有利な特性のため近年需要が急速に増加しつつある。 The printed circuit board may be a rigid printed circuit board, a flexible printed circuit board, a rigid-bonded printed circuit board, a multi-layer similar to a rigid-flexible printed circuit board, or the like. Divided into flexible printed circuit boards. In particular, flexible copper clad laminate (FCCL), which is a raw material for flexible printed circuit boards, is used in digital home appliances such as mobile phones, digital camcorders, notebook computers, and LCD monitors. In recent years, demand has been rapidly increasing due to its great flexibility and advantageous properties for lightness, thinness, and miniaturization.
軟性銅箔積層板（ＦＣＣＬ）は、ポリマーフィルム層及び金属伝導層を積層したものであって、可撓性を有することが特徴である。軟性銅張積層板は、特に柔軟性や屈曲性が求められる電子機器または電子機器の素材部分に用いられ、電子機器の小型化、軽量化に寄与している。 A flexible copper foil laminate (FCCL) is a laminate of a polymer film layer and a metal conductive layer, and is characterized by having flexibility. The flexible copper clad laminate is used for an electronic device or a material part of the electronic device that is particularly required to have flexibility and flexibility, and contributes to the reduction in size and weight of the electronic device.
このような軟性銅箔積層板（または一般の銅箔積層板（ＣＣＬ））は、樹脂フィルムの両面に、電着法などを用いて製造された電解銅箔をロールプレスすることで得られる。 Such a soft copper foil laminated board (or general copper foil laminated board (CCL)) is obtained by roll-pressing the electrolytic copper foil manufactured using the electrodeposition method etc. on both surfaces of the resin film.
但し、このようなロールプレスによる軟性銅箔積層板（または銅箔積層板）の製造過程で接触面において発生するスリップ（ｓｌｉｐ）現象や銅箔に発生するしわ及び／または押し傷により歩留まりが減少し、製品の品質が低下する問題点があり、これを解決するための技術が求められている。 However, the yield is reduced due to slip phenomenon that occurs on the contact surface in the process of manufacturing a flexible copper foil laminate (or copper foil laminate) by such a roll press, and wrinkles and / or scratches that occur on the copper foil. However, there is a problem that the quality of the product is lowered, and a technique for solving this problem is required.
本発明は、上記問題点に鑑みてなされたものであり、銅箔の両表面のうち樹脂フィルムが付着されない外側面のＳＣ因子を一定水準に調節することで、銅箔積層板と樹脂フィルムとのラミネイティング過程でロールと銅箔との接触面上で発生するスリップ現象を最小化することによって、銅箔積層板の歩留まりを上昇させるだけでなく、銅箔に発生するしわ及び／または押し傷を防止することで、製造される銅箔積層板の品質を向上させることを一目的とする。 The present invention has been made in view of the above problems, and by adjusting the SC factor of the outer surface to which the resin film is not attached among both surfaces of the copper foil to a certain level, the copper foil laminate and the resin film By minimizing the slip phenomenon occurring on the contact surface between the roll and the copper foil during the laminating process, not only the yield of the copper foil laminate is increased, but also wrinkles and / or scratches generated in the copper foil. It aims at improving the quality of the manufactured copper foil laminated board by preventing.
但し、本発明が有する効果はこれに限定されず、ここに説明されていない本発明による効果は、以下に説明する本発明の図面及び発明の詳細な説明からより明確に理解されるだろう。 However, the effect of the present invention is not limited to this, and the effect of the present invention not described here will be understood more clearly from the drawings of the present invention and the detailed description of the invention described below.
上記の課題を達成するため、銅箔の両表面のうち樹脂フィルムが付着されない外側面のＳＣ因子を一定水準に調節することで、銅箔積層板の歩留まりを向上させるだけでなく、銅箔に発生するしわ及び／または押し傷を防止することで、製造される銅箔積層板の品質を向上させることができる電解銅箔を開発した。 In order to achieve the above-mentioned problem, not only the yield of the copper foil laminate is improved but also the copper foil is adjusted by adjusting the SC factor of the outer surface of the copper foil to which the resin film is not attached to a certain level. The electrolytic copper foil which can improve the quality of the manufactured copper foil laminated board by preventing the wrinkles and / or a press wound which generate | occur | produced was developed.
このように、優れる特性を有する本発明の一実施例による電解銅箔は、銅箔積層板の製造に用いられる電解銅箔であって、樹脂フィルムが付着されない第１面が有する表面因子ＳＣ値が２．２１乃至４．０９の範囲であり、前記表面因子ＳＣは、前記第１面が有する測定単位面積に対する実表面積の比（ｒａｔｉｏ）である。 Thus, the electrolytic copper foil according to an embodiment of the present invention having excellent characteristics is an electrolytic copper foil used for the manufacture of a copper foil laminate, and has a surface factor SC value that the first surface has no resin film attached thereto. Is in the range of 2.21 to 4.09, and the surface factor SC is a ratio of the actual surface area to the measurement unit area of the first surface.
前記電解銅箔の両面のうち、前記樹脂フィルムが付着される第２面には、亜鉛、亜鉛合金、クロム、クロム合金、亜鉛酸化物及びクロム酸化物を含む群より選択された一つ以上の材質からなる保護層が備えられ得る。 Of the two surfaces of the electrolytic copper foil, the second surface to which the resin film is attached is at least one selected from the group comprising zinc, zinc alloy, chromium, chromium alloy, zinc oxide and chromium oxide. A protective layer made of a material may be provided.
なお、電解銅箔の両面のうち、前記樹脂フィルムが付着される第２面には樹脂フィルムとの物理的な接着力の確保のための銅ノジュール層が形成され得、このようなノジュール層は、電解銅箔の第２面上に銅ノジュールの核を形成した後、これを成長させるめっき処理によって形成され得る。 In addition, the copper nodule layer for ensuring physical adhesive force with a resin film may be formed in the 2nd surface where the said resin film adheres among both surfaces of electrolytic copper foil, and such a nodule layer is After forming a copper nodule nucleus on the second surface of the electrolytic copper foil, it can be formed by a plating process for growing the core.
前記電解銅箔の両面のうち、前記樹脂フィルムが付着される第２面には、Ｎｉ、Ｃｏ及びＭｏを含む群より選択された材質からなる少なくとも１層以上のバリアー層が備えられ得る。 Of the two surfaces of the electrolytic copper foil, the second surface to which the resin film is attached may be provided with at least one or more barrier layers made of a material selected from the group including Ni, Co, and Mo.
前記電解銅箔の両面のうち、前記樹脂フィルムが付着される第２面が有する平均粗さ（Ｒａ）は、０超過０．８μｍ未満である得る。 Of the two surfaces of the electrolytic copper foil, the average roughness (Ra) of the second surface to which the resin film is attached may be greater than 0 and less than 0.8 μm.
前記電解銅箔の両面のうち、前記樹脂フィルムが付着される第２面には、Ｓｉ化合物層が備えられ得る。 Of the two surfaces of the electrolytic copper foil, a Si compound layer may be provided on a second surface to which the resin film is attached.
前記電解銅箔の厚さは、０μｍ超過１０５μｍ以下であり得る。 The thickness of the electrolytic copper foil may be more than 0 μm and not more than 105 μm.
前記第１面は、銅箔製造の際し、ドラムに接しない銅箔面であり得る。 The first surface may be a copper foil surface that is not in contact with the drum during the manufacture of the copper foil.
なお、本発明の一実施例によるＦＣＣＬ及びＣＣＬには、前記電解銅箔が適用され、同様に、本発明の一実施例による印刷回路基板には前記ＦＣＣＬ及びＣＣＬが適用される。 In addition, the said electrolytic copper foil is applied to FCCL and CCL by one Example of this invention, and said FCCL and CCL are similarly applied to the printed circuit board by one Example of this invention.
前記ＦＣＣＬ及びＣＣＬに適用される樹脂層は、ポリイミド材質からなり得る。 The resin layer applied to the FCCL and CCL may be made of a polyimide material.
本発明の一面によれば、銅箔の両表面のうち樹脂フィルムが付着しない外側面のＳＣ因子を一定水準に調節することで、銅箔積層板と樹脂フィルムとのラミネイティング過程でロール及び銅箔の接触面において発生するスリップ現象を最小化することによって、銅箔積層板の歩留まりを上昇させることができる。 According to one aspect of the present invention, by adjusting the SC factor of the outer surface of the both surfaces of the copper foil to which the resin film does not adhere to a certain level, the roll and copper are laminated in the lamination process between the copper foil laminate and the resin film. By minimizing the slip phenomenon that occurs on the contact surface of the foil, the yield of the copper foil laminate can be increased.
なお、本発明の他面によれば、銅箔に発生するしわ及び／または押し傷を防止することで、製造される銅箔積層板の品質を向上させることができる。 In addition, according to the other surface of this invention, the quality of the manufactured copper foil laminated board can be improved by preventing the wrinkles and / or a press wound which generate | occur | produce in copper foil.
以下、添付された図面を参照して本発明の望ましい実施例を詳しく説明する。これに先立ち、本明細書及び請求範囲に使われた用語や単語は通常的や辞書的な意味に限定して解釈されてはならず、発明者自らは発明を最善の方法で説明するために用語の概念を適切に定義できるという原則に則して本発明の技術的な思想に応ずる意味及び概念で解釈されねばならない。したがって、本明細書に記載された実施例及び図面に示された構成は、本発明のもっとも望ましい一実施例に過ぎず、本発明の技術的な思想のすべてを代弁するものではないため、本出願の時点においてこれらに代替できる多様な均等物及び変形例があり得ることを理解せねばならない。 Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, the terms and words used in this specification and claims should not be construed to be limited to ordinary or lexicographic meanings, and the inventor himself should explain the invention in the best possible manner. It must be interpreted with the meaning and concept corresponding to the technical idea of the present invention in accordance with the principle that the term concept can be appropriately defined. Therefore, the configuration described in the embodiments and drawings described in this specification is only the most preferable embodiment of the present invention, and does not represent all of the technical idea of the present invention. It should be understood that there may be various equivalents and variations that can be substituted for at the time of filing.
図１を参照して本発明の一実施例による電解銅箔１を説明する。 With reference to FIG. 1, the electrolytic copper foil 1 by one Example of this invention is demonstrated.
図１は、本発明の一実施例による電解銅箔を示す図である。 FIG. 1 is a view showing an electrolytic copper foil according to an embodiment of the present invention.
図１を参照すれば、電気めっきによって製造される本発明の一実施例による電解銅箔１は、約１０５μｍ以下の厚さを有するものを用いることができる。 Referring to FIG. 1, an electrolytic copper foil 1 manufactured by electroplating according to an embodiment of the present invention may have a thickness of about 105 μm or less.
ここで、第１面１ａは外側に露出する面であり、第２面１ｂはその反対側に位置する面であって、ＦＣＣＬまたはＣＣＬの製造時に樹脂フィルムが付着される面である。 Here, the 1st surface 1a is a surface exposed outside, and the 2nd surface 1b is a surface located in the other side, Comprising: A resin film adheres at the time of manufacture of FCCL or CCL.
前記第２面１ｂ上には、絶縁のための樹脂層２が形成され、該樹脂層２は、例えば、ポリイミド（ＰＩ：Ｐｏｌｙｉｍｉｄｅ）のような材質からなり得る。 A resin layer 2 for insulation is formed on the second surface 1b, and the resin layer 2 may be made of a material such as polyimide (PI).
このような電解銅箔１は、電解槽内に回転ドラム及びドラムに対し所定間隔を置いて位置する正極板を含む構造の製箔機を用いて製造されるものであって、通常、硫酸銅を電解液にして約１０Ａ／ｄｍ２ないし８０Ａ／ｄｍ２範囲の電流密度でドラム上に銅を電着して製造される。この際、電解銅泊は、回転ドラムに接する光沢面と回転ドラムに接しないマット面とで両面が構成される。 Such an electrolytic copper foil 1 is manufactured using a foil making machine having a structure including a rotating drum and a positive electrode plate positioned at a predetermined interval with respect to the drum in an electrolytic cell, and is usually copper sulfate. from about 10A / dm 2 not in the electrolytic solution is prepared by electrodeposition of copper on the drum at a current density of 80A / dm 2 ranges. At this time, the electrolytic copper stay is composed of both a glossy surface in contact with the rotating drum and a mat surface not in contact with the rotating drum.
なお、前記電解銅箔１は、第１面１ａが有する表面因子ＳＣの値が約２．２１ないし４．０９の範囲に制限されることが望ましい。 In addition, as for the said electrolytic copper foil 1, it is desirable that the value of the surface factor SC which the 1st surface 1a has is restrict | limited to the range of about 2.21 to 4.09.
このような表面因子ＳＣは、第１面１ａを対象として３次元に測定された実表面積を、該面の平面視面積（測定単位面積）で割った値である。また、前記実表面積とは、銅箔試料の第１面１ａにおける測定領域を３Ｄ顕微鏡で３次元的に測定して得られる面積であり、具体的には、３Ｄ顕微鏡レンズをＺ軸方向に移動させて焦点を移動させることで得られる面積である。即ち、前記表面因子ＳＣは、前記露出面が有する測定単位面積に対する実表面積の比である。 Such a surface factor SC is a value obtained by dividing the actual surface area measured three-dimensionally for the first surface 1a by the planar view area (measurement unit area) of the surface. The actual surface area is an area obtained by three-dimensionally measuring the measurement region on the first surface 1a of the copper foil sample with a 3D microscope. Specifically, the 3D microscope lens is moved in the Z-axis direction. The area obtained by moving the focal point. That is, the surface factor SC is the ratio of the actual surface area to the measurement unit area of the exposed surface.
本実施例では、銅箔の試片を１×１ｃｍ正方形に取り、３Ｄ顕微鏡で観察して測定した。また、３Ｄ顕微鏡の倍率は、２００ないし２０００倍の範囲内で測定しても構わないが、本実施例では５００倍で測定した。 In this example, a copper foil specimen was taken in a 1 × 1 cm square and measured by observation with a 3D microscope. Further, the magnification of the 3D microscope may be measured within a range of 200 to 2000 times, but in this example, it was measured at 500 times.
ここで、表面積の測定のための３Ｄ顕微鏡としては、３Ｄ解析の可能なレーザー顕微鏡であって前記表面積及び面積が測定可能なものであれば、特に限定されない。この３Ｄ顕微鏡に用いられるレーザーは、可視光限界波長４０５ｎｍないし４１０ｎｍのバイオレットレーザーであれば、ＳＣ因子を精度よく測定可能であるため、望ましい。 Here, the 3D microscope for measuring the surface area is not particularly limited as long as it is a laser microscope capable of 3D analysis and capable of measuring the surface area and area. If the laser used for this 3D microscope is a violet laser with a visible light limit wavelength of 405 nm to 410 nm, it is desirable because the SC factor can be accurately measured.
なお、本発明において測定区域の現状は特に限定されないが、例えば、正方形、直方形などの形状であり得る。 In the present invention, the current state of the measurement area is not particularly limited, but may be, for example, a square or a rectangular shape.
このようなＳＣ因子は、電解銅箔１の製造のための製箔工程にて適用される添加剤の種類及び含量範囲、めっき液の温度（４０ないし６０℃）、めっき液の組成（銅は６０ないし１００ｇ／Ｌ、硫酸は８０〜１３０ｇ／Ｌ）、めっきのときに印加される電流密度（１０〜８０Ａ／ｄｍ２）及び製箔機のドラム研磨条件などに係わる。 Such SC factors include the type and content range of additives applied in the foil-making process for the production of the electrolytic copper foil 1, the temperature of the plating solution (40 to 60 ° C.), the composition of the plating solution (copper is 60 to 100 g / L, sulfuric acid is 80 to 130 g / L), current density applied during plating (10 to 80 A / dm 2 ), drum machine polishing conditions, and the like.
例えば、めっき添加剤として使用可能なハイドロキシエチルセルロース（ｈｙｄｒｏｘｙｅｔｈｙｌ ｃｅｌｌｕｌｏｓｅ）、ゼラチン（ｇｅｌａｔｉｎ）、コラーゲン（ｃｏｌｌａｇｅｎ）及び塩素のうちいずれを選択するかの選択如何、及び該選択物質のめっき液内での濃度などを調節（ハイドロキシエチルセルロースは２〜５ｐｐｍ、ゼラチン及びコラーゲンは２〜４ｐｐｍ、塩素は１０〜２０ｐｐｍの範囲内で調節）することによって、第１面１ａのＳＣ因子値を制御することができ、更に、めっき液の濃度及び組成などをともに変更して電解銅箔１の第１面１ａが有するＳＣ因子値を制御することができる。 For example, whether to select hydroxyethyl cellulose, gelatin, collagen, or chlorine that can be used as a plating additive, and the concentration of the selected substance in the plating solution, etc. By adjusting (in the range of 2 to 5 ppm for hydroxyethyl cellulose, 2 to 4 ppm for gelatin and collagen, and 10 to 20 ppm for chlorine), the SC factor value of the first surface 1a can be controlled, The SC factor value of the first surface 1a of the electrolytic copper foil 1 can be controlled by changing both the concentration and composition of the plating solution.
なお、ＳＣ因子値に影響を及ぼすさまざまな要素の中、ドラム研磨条件に関しては、ドラムをブラシ（ｂｒｕｓｈ）でバフィングするとき、研磨＃、バフィング圧力、バフィング回転速度及び振動速度を調節することで、ＳＣ因子を制御することができる。すなわち、ブラシの研磨＃は６００〜２０００、バフィング圧力は０．５〜５．０Ａｍｐｅｒｅ、回転速度は５０〜３５０ｒｐｍ、振動速度は５０〜２５０ｃｐｍ範囲で調節することで、本発明の実施例によるＳＣ因子を満す銅箔を製造することができる。 Among the various factors that affect the SC factor value, regarding drum polishing conditions, when buffing the drum with a brush, adjusting polishing #, buffing pressure, buffing rotation speed, and vibration speed, SC factor can be controlled. In other words, the brush polishing # is 600 to 2000, the buffing pressure is 0.5 to 5.0 Ampere, the rotation speed is 50 to 350 rpm, and the vibration speed is adjusted in the range of 50 to 250 cpm, so that the SC factor according to the embodiment of the present invention. Can be produced.
ＳＣ因子値に影響を及ぼすさまざまな要素を異にして製造した本発明の実施例１〜９による電解銅泊及び比較例１〜９による電解銅泊それぞれの製造条件は、以下の表１に示し、それぞれのドラム研磨条件は表２に示した。
The production conditions of the electrolytic copper stays according to Examples 1 to 9 of the present invention and the electrolytic copper stays according to Comparative Examples 1 to 9 manufactured with different factors affecting the SC factor value are shown in Table 1 below. The respective drum polishing conditions are shown in Table 2.
なお、前記ＳＣ因子値の制御による利点については、表３に示した実施例及び比較例を通じて詳しく後述する。 The advantages of controlling the SC factor value will be described later in detail through examples and comparative examples shown in Table 3.
続いて、前記電解銅箔１の第２面１ｂについて説明すれば、電解銅箔１の第２面１ｂが有する平均粗さＲａが高すぎる場合は、電解銅箔１を用いた銅導線パターンの形成時に残銅（エッチングによるパターン形成後、銅箔成分が完全に除去されるべき部分に銅箔成分が残る現象）が発生し得る。したがって、このような残銅発生の防止のために、第２面１ｂが有する平均粗度Ｒａは、０μｍ超過０．８μｍ未満の範囲に制限されることが望ましい。 Then, if the 2nd surface 1b of the said electrolytic copper foil 1 is demonstrated, when the average roughness Ra which the 2nd surface 1b of the electrolytic copper foil 1 has is too high, of the copper conducting wire pattern using the electrolytic copper foil 1 Residual copper (a phenomenon in which the copper foil component remains in a portion where the copper foil component should be completely removed after pattern formation by etching) may occur during formation. Therefore, in order to prevent such residual copper generation, it is desirable that the average roughness Ra of the second surface 1b is limited to a range of more than 0 μm and less than 0.8 μm.
なお、前記電解銅箔１は、上述の電着工程によって製造された銅ホイルの第２面１ｂ上に形成される一つ以上の機能性層を備えてもよく、このような機能性層としては、銅ノジュール層、保護層、バリアー層、シランカップリング層などが挙げられる。 In addition, the said electrolytic copper foil 1 may be equipped with one or more functional layers formed on the 2nd surface 1b of the copper foil manufactured by the above-mentioned electrodeposition process, As such a functional layer, Examples thereof include a copper nodule layer, a protective layer, a barrier layer, and a silane coupling layer.
より具体的に、前記電解銅箔１の第２面１ｂ上にこれらの機能性層が形成される場合、銅ノジュール層及び／または保護層及び／またはバリアー層（保護層及びバリアー層のいずれも存在する場合、その積層順序は構わない） 及び／またはラインカップリング層の手順に積層され得る。 More specifically, when these functional layers are formed on the second surface 1b of the electrolytic copper foil 1, a copper nodule layer and / or a protective layer and / or a barrier layer (both of the protective layer and the barrier layer) If present, the stacking order is irrelevant) and / or may be stacked in a line coupling layer procedure.
前記銅ノジュール層は、樹脂フィルム２との物理的な接着力の確保のために樹脂に接触する電解銅箔１の第２面１ｂ上に銅ノジュールの核を形成した後、これを成長させるめっき処理によって形成される。 The copper nodule layer is formed by forming a copper nodule nucleus on the second surface 1b of the electrolytic copper foil 1 in contact with the resin in order to ensure physical adhesion with the resin film 2, and then growing the copper nodule layer. Formed by processing.
前記保護層は、例えば、亜鉛（Ｚｎ）、亜鉛合金、クロム（Ｃｒ）、クロム合金、亜鉛酸化物またはクロム酸化物からなる層であって、通常、銅製箔工程の後に行われるめっき工程によって形成されることにより、銅箔の熱酸化を防止し、防錆効果を奏する。 The protective layer is, for example, a layer made of zinc (Zn), zinc alloy, chromium (Cr), chromium alloy, zinc oxide or chromium oxide, and is usually formed by a plating process performed after the copper foil process. As a result, thermal oxidation of the copper foil is prevented, and an antirust effect is exhibited.
前記バリアー層は、銅箔から銅が拡散することを抑制し、銅箔の安定性を確保するために電解銅箔１の第２面１ｂに備えられるものであって、例えば、ニッケル（Ｎｉ）、コバルト（Ｃｏ）、モリブデン（Ｍｏ）などの金属からなり得る。勿論、このようなバリアー層は、前述の銅ノジュール層及び／または保護層が先に形成された後、その上にともに形成され得る。なお、このようなバリアー層は、一つの層として形成され得、二つ以上のバリアー層として形成されることもある。 The barrier layer is provided on the second surface 1b of the electrolytic copper foil 1 to suppress copper diffusion from the copper foil and to ensure the stability of the copper foil. For example, nickel (Ni) , Cobalt (Co) and molybdenum (Mo). Of course, such a barrier layer may be formed on the copper nodule layer and / or the protective layer after the copper nodule layer and the protective layer are first formed. In addition, such a barrier layer can be formed as one layer, and may be formed as two or more barrier layers.
前記シランカップリング層はＳｉ化合物からなる層であって、電解銅箔１と樹脂フィルム２との化学的接着力を確保するために電解銅箔１の第２面１ｂに備えられ得る。このようなシランカップリング層は、前述の銅ノジュール層及び／または保護層及び／またはバリアー層が形成された後、その上にともに形成され得る。 The silane coupling layer is a layer made of a Si compound, and may be provided on the second surface 1 b of the electrolytic copper foil 1 in order to ensure chemical adhesion between the electrolytic copper foil 1 and the resin film 2. Such a silane coupling layer can be formed together on the copper nodule layer and / or protective layer and / or barrier layer described above.
以下、表３を参照して前記電解銅箔１の第１面１ａが有するＳＣ因子値の制御による効果について説明する。 Hereinafter, with reference to Table 3, the effect by control of the SC factor value which the 1st surface 1a of the said electrolytic copper foil 1 has is demonstrated.
本実施例及び比較例に示す両面ＦＣＣＬサンプルは、ＰＩフィルムの両面に銅箔を投入して窒素雰囲気下でロールプレスによって製作され、ここでロールプレスは約３６０℃で行われた。 The double-sided FCCL samples shown in the examples and comparative examples were manufactured by roll pressing in a nitrogen atmosphere with copper foils placed on both sides of the PI film, where the roll pressing was performed at about 360 ° C.
また、ＦＣＣＬ製造線速を通常の製造方法である４ｍｐｍにしてＳＣ因子による外観不良の発生有無を測定した。 Also, the occurrence of appearance defects due to the SC factor was measured by setting the FCCL production line speed to 4 mpm, which is a normal production method.
前記表３を参照すれば、電解銅箔１の第１ 面１ａが有するＳＣ因子値が約２．２１〜４．０９の範囲内である場合、電解銅箔１の品質が優秀に維持されることが分かる。 Referring to Table 3, when the SC factor value of the first surface 1a of the electrolytic copper foil 1 is within the range of about 2.21 to 4.09, the quality of the electrolytic copper foil 1 is maintained excellent. I understand that.
すなわち、樹脂フィルム２の両面にラミネイティングロールプレスを適用して両面ＦＣＣＬの製作に際し、ＳＣ因子が２．２１未満の場合は、ラミネイティングロールと電解銅箔１との間にスリップが発生して電解銅箔１にしわが発生する。 That is, when producing a double-sided FCCL by applying a laminating roll press to both sides of the resin film 2, if the SC factor is less than 2.21, slip occurs between the laminating roll and the electrolytic copper foil 1. Wrinkles are generated in the electrolytic copper foil 1.
このようなＳＣ因子の制御によるしわの発生有無は、特に実施例６と比較例９とを見れば明確に分かり、実施例１の結果を示す図２と比較例１の結果を示す図３との比較からも確認することができる。 The presence or absence of wrinkles due to the control of the SC factor can be clearly seen particularly by looking at Example 6 and Comparative Example 9, FIG. 2 showing the result of Example 1 and FIG. 3 showing the result of Comparative Example 1. This can also be confirmed from the comparison.
また、同様に、ラミネイティングロールプレスを適用した両面ＦＣＣＬの製作に際し、ＳＣ因子が４．０９を超過する場合は、ラミネイティングのときに電解銅箔１に押し傷が発生する。 Similarly, when producing a double-sided FCCL to which a laminating roll press is applied, if the SC factor exceeds 4.09, the electrolytic copper foil 1 is scratched during laminating.
このようなＳＣ因子の制御による押し傷の発生有無は、特に実施例７の結果を示す図４と比較例５の結果を示す図５との比較から確認することができる。 The presence / absence of the occurrence of such a press wound by the control of the SC factor can be confirmed particularly from the comparison between FIG. 4 showing the result of Example 7 and FIG. 5 showing the result of Comparative Example 5.
上述したように、本発明の一実施例による電解銅箔１は、樹脂フィルム２が付着しない面が有するＳＣ因子の値を一定範囲内に制御することで、高い線速で不良なく銅箔を樹脂フィルムに接着するようにする。 As described above, the electrolytic copper foil 1 according to one embodiment of the present invention controls the SC factor value of the surface to which the resin film 2 does not adhere within a certain range, so that the copper foil can be obtained without defects at a high linear velocity. Adhere to the resin film.
すなわち、本発明による電解銅箔１によれば、ポリイミド（ＰＩ）のような樹脂フィルム２の両面に電解銅箔１をラミネイティングして製造されるＦＣＣＬを製造する過程で、電解銅箔１にしわ及び／または押し傷が発生することを防止できるため、優秀な品質のＦＣＣＬを高い歩留まりで生産することができる。 That is, according to the electrolytic copper foil 1 of the present invention, in the process of manufacturing FCCL produced by laminating the electrolytic copper foil 1 on both surfaces of a resin film 2 such as polyimide (PI), Since the generation of wrinkles and / or pressing flaws can be prevented, excellent quality FCCL can be produced with a high yield.
なお、このような電解銅箔１が両面ＦＣＣＬに適用される場合のみならず、片面ＦＣＣＬまたはＣＣＬに適用される場合にも、しわ及び／または押し傷の発生を防止することができることは勿論である。 In addition, when such an electrolytic copper foil 1 is applied not only to the double-sided FCCL but also to the single-sided FCCL or CCL, it is of course possible to prevent the generation of wrinkles and / or pressing flaws. is there.
以上のように、本発明を限定された実施例と図面によって説明したが、本発明はこれに限定されるものではなく、本発明の属する技術分野で通常の知識を持つ者によって本発明の技術思想と特許請求の範囲の均等範囲内で多様な修正及び変形が可能であることは言うまでもない。 As described above, the present invention has been described with reference to the limited embodiments and drawings. However, the present invention is not limited to this, and the technology of the present invention can be obtained by those who have ordinary knowledge in the technical field to which the present invention belongs. It goes without saying that various modifications and variations can be made within the scope of the idea and the scope of claims.
１：電解銅箔 １ａ：第１面（露出面）
１ｂ：第２面（付着面） ２：樹脂フィルム
1: Electrolytic copper foil 1a: First surface (exposed surface)
1b: Second surface (attachment surface) 2: Resin film
Claims (9)
樹脂フィルムが付着されない第１面が有する表面因子ＳＣ値が２．２１乃至４．０９の範囲であり、
前記表面因子ＳＣは、前記第１面が有する測定単位面積に対する実表面積の比である電解銅箔。 An electrolytic copper foil used in the manufacture of a copper foil laminate,
The surface factor SC value of the first surface to which the resin film is not attached is in the range of 2.21 to 4.09,
The surface factor SC is an electrolytic copper foil that is a ratio of an actual surface area to a measurement unit area of the first surface.
前記電解銅箔の第２面に形成される樹脂フィルムと、を含むＦＣＣＬ。 An electrolytic copper foil according to any one of claims 1 to 7,
And a resin film formed on the second surface of the electrolytic copper foil.
前記電解銅箔の第２面に形成される樹脂フィルムと、を含むＣＣＬ。 An electrolytic copper foil according to any one of claims 1 to 7,
And a resin film formed on the second surface of the electrolytic copper foil.
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| KR1020150124837A KR102392045B1 (en) | 2014-12-23 | 2015-09-03 | Electrolytic copper foil, and FCCL and CCL comprising the same |
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| JP5242710B2 (en) * | 2010-01-22 | 2013-07-24 | 古河電気工業株式会社 | Roughening copper foil, copper clad laminate and printed wiring board |
| JP5128695B2 (en) * | 2010-06-28 | 2013-01-23 | 古河電気工業株式会社 | Electrolytic copper foil, electrolytic copper foil for lithium ion secondary battery, electrode for lithium ion secondary battery using the electrolytic copper foil, lithium ion secondary battery using the electrode |
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2015
- 2015-12-01 JP JP2015234546A patent/JP2016121394A/en active Pending
- 2015-12-23 CN CN201510977729.9A patent/CN105714336A/en active Pending
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| JP2004256910A (en) * | 2003-02-04 | 2004-09-16 | Furukawa Techno Research Kk | Copper foil for high-frequency circuit, manufacturing method therefor, manufacturing facility therefor, and high-frequency circuit using the copper foil |
| JP2008179127A (en) * | 2007-01-15 | 2008-08-07 | Ls Cable Ltd | Copper foil laminate and method for treating surface of copper foil |
| JP2009164488A (en) * | 2008-01-09 | 2009-07-23 | Hitachi Cable Ltd | Copper foil for a printed wiring board |
| WO2013002279A1 (en) * | 2011-06-30 | 2013-01-03 | 古河電気工業株式会社 | Electrolytic copper foil, method for producing electrolytic copper foil, and lithium ion secondary cell using electrolytic copper foil as collector |
| JP2013147688A (en) * | 2012-01-18 | 2013-08-01 | Jx Nippon Mining & Metals Corp | Surface-treated copper foil for use in copper-clad laminated board, and copper-clad laminated board employing the same |
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| CN105714336A (en) | 2016-06-29 |
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