JP5705381B2 - Blackened surface-treated copper foil, method for producing blackened surface-treated copper foil, copper-clad laminate and flexible printed wiring board - Google Patents
Blackened surface-treated copper foil, method for producing blackened surface-treated copper foil, copper-clad laminate and flexible printed wiring board Download PDFInfo
- Publication number
- JP5705381B2 JP5705381B2 JP2014532134A JP2014532134A JP5705381B2 JP 5705381 B2 JP5705381 B2 JP 5705381B2 JP 2014532134 A JP2014532134 A JP 2014532134A JP 2014532134 A JP2014532134 A JP 2014532134A JP 5705381 B2 JP5705381 B2 JP 5705381B2
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- wiring board
- printed wiring
- flexible printed
- black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 285
- 239000011889 copper foil Substances 0.000 title claims description 187
- 238000004519 manufacturing process Methods 0.000 title claims description 56
- 229910052802 copper Inorganic materials 0.000 claims description 97
- 239000010949 copper Substances 0.000 claims description 97
- 238000007788 roughening Methods 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000008151 electrolyte solution Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 238000004381 surface treatment Methods 0.000 claims description 15
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 description 45
- 238000005530 etching Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- 230000008569 process Effects 0.000 description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 15
- 230000002265 prevention Effects 0.000 description 15
- 238000007689 inspection Methods 0.000 description 13
- 239000006087 Silane Coupling Agent Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 239000009719 polyimide resin Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/028—Electroplating of selected surface areas one side electroplating, e.g. substrate conveyed in a bath with inhibited background plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0692—Regulating the thickness of the coating
-
- 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
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- 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
-
- 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
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Structure Of Printed Boards (AREA)
- ing And Chemical Polishing (AREA)
Description
本件出願は、黒色化表面処理銅箔、黒色化表面処理銅箔の製造方法、黒色化表面処理銅箔を用いて得られる銅張積層板及びフレキシブルプリント配線板に関する。特に、銅箔の表面に黒色化する微細な粗化処理を行った表面処理銅箔に関する。 The present application relates to a blackened surface-treated copper foil, a method for producing a blackened surface-treated copper foil, a copper-clad laminate and a flexible printed wiring board obtained using the blackened surface-treated copper foil. It is related with the surface-treated copper foil which performed the fine roughening process which blackens on the surface of copper foil especially.
従来から、プリント配線板の自動外観検査機として、ＡＯＩ（Ａｕｔｏｍａｔｉｃ Ｏｐｔｉｃａｌ Ｉｎｓｐｅｃｔｅｒ）が自動検査に広く使用されてきた。ＡＯＩは、プリント配線板の背面から光を投光して、当該プリント配線板を透過する光を捉え、回路パターンを読み取ることにより、仕様を逸脱した、パターン欠け、パターン細り、ピンホール、傷、ショート、パターン太り、銅残り、突起、汚れ等の回路欠陥を発見する装置である。 Conventionally, AOI (Automatic Optical Inspector) has been widely used for automatic inspection as an automatic visual inspection machine for printed wiring boards. AOI emits light from the back of the printed wiring board, captures the light transmitted through the printed wiring board, and reads the circuit pattern, thereby deviating from the specification, pattern chipping, pattern thinning, pinholes, scratches, It is a device that detects circuit defects such as shorts, pattern thickening, copper residue, protrusions, and dirt.
また、近年は、液晶ディスプレイモジュールとフレキシブルプリント配線板とを異方性導電膜（ＡＣＦ）で接続する際に、液晶ディスプレイモジュールの接続端子とフレキシブルプリント配線板の接続端子とを、フレキシブルプリント配線板の回路背面からＣＣＤカメラを用いて位置合わせすることが行われている。そのため、回路背面と樹脂フィルムとの間に、色調として明瞭なコントラストが存在することが望ましい。従って、一般的には、回路形成に用いる銅箔の樹脂フィルムとの接着面が、良好な黒色であることが求められる。一方、フレキシブルプリント配線板の銅箔をエッチング除去して露出した樹脂フィルムには、良好な視認性が求められる。この視認性（以下、単に「ＣＣＤ視認性」と称する。）は、フレキシブルプリント配線板の銅箔をエッチング除去して露出した樹脂フィルムの曇り度（Ｈａｚｅ）に依存する。 In recent years, when the liquid crystal display module and the flexible printed wiring board are connected by an anisotropic conductive film (ACF), the connection terminal of the liquid crystal display module and the connecting terminal of the flexible printed wiring board are connected to the flexible printed wiring board. Positioning is performed from the back of the circuit using a CCD camera. Therefore, it is desirable that a clear contrast exists as a color tone between the circuit back surface and the resin film. Therefore, generally, it is required that the adhesive surface of the copper foil used for circuit formation with the resin film is a good black color. On the other hand, good visibility is required for the resin film exposed by etching away the copper foil of the flexible printed wiring board. This visibility (hereinafter simply referred to as “CCD visibility”) depends on the haze of the resin film exposed by etching away the copper foil of the flexible printed wiring board.
従って、上述の用途において、フレキシブルプリント配線板のＣＣＤ視認性及びＡＯＩの検査精度を向上させるためには、「フレキシブルプリント配線板の銅箔をエッチング除去して露出した樹脂フィルムが光透過性に優れること。」、「回路背面の色調と樹脂フィルムとの色調の差が明瞭であること。」等の特性が要求される。即ち、前者は、銅張積層板の銅箔をエッチング除去して露出した樹脂フィルムの曇り度（Ｈａｚｅ）の値が低いという特性を要求するものであり、銅箔の接着面が樹脂フィルム表面に残す凹凸形状に左右される特性である。そして、後者は、銅箔の樹脂フィルムとの接着面が備える色調に左右される特性である。これらの要求特性を満足する銅箔として、以下の特許文献１、特許文献２に開示の表面処理銅箔が挙げられる。 Therefore, in the above-mentioned application, in order to improve the CCD visibility of the flexible printed wiring board and the AOI inspection accuracy, “the resin film exposed by etching away the copper foil of the flexible printed wiring board is excellent in light transmittance. The characteristics such as “the difference between the color tone of the circuit back surface and the color tone of the resin film is clear” are required. That is, the former requires the property that the resin film exposed by etching away the copper foil of the copper clad laminate has a low haze value, and the adhesive surface of the copper foil is on the resin film surface. This characteristic depends on the uneven shape to be left. And the latter is a characteristic influenced by the color tone with which the adhesion surface with the resin film of copper foil is provided. Examples of the copper foil satisfying these required characteristics include surface-treated copper foils disclosed in Patent Document 1 and Patent Document 2 below.
特許文献１には、フレキシブル銅張積層板の銅層形成に用いる銅箔であって、ファインピッチ回路形成が可能で、加熱後の接着強度が良好な表面処理銅箔の提供を目的としたものであり、「ポリイミド樹脂層の表面に銅層を形成するための銅箔において、当該銅箔はポリイミド樹脂層との接着面に、コバルト層又はコバルト層とニッケル−亜鉛合金層とが積層した状態のいずれかの表面処理層を備えることを特徴とするフレキシブル銅張積層板製造用の表面処理銅箔を採用する。」ことが開示され、無粗化の表面処理銅箔を対象としている。この特許文献１の明細書の段落００３４には「更に、当該表面処理銅箔のポリイミド樹脂基材との接着面は、光沢度［Ｇｓ（６０°）］が７０以上である事が好ましい。良好なファインピッチ回路形成能及び光学式自動検査（ＡＯＩ検査）のときに求められる良好な光透過性を確保するためである。例えば、・・・（途中省略）・・・。本件発明では、光沢度［Ｇｓ（６０°）］が７０以上としているが、光沢度が７０未満の場合には、良好なファインピッチ回路形成能が得られず、光学式自動検査装置（ＡＯＩ装置）による検査時に求められる良好な光透過性の確保も困難となる。」との記載がある。 Patent Document 1 discloses a copper foil used for forming a copper layer of a flexible copper-clad laminate, and is intended to provide a surface-treated copper foil capable of forming a fine pitch circuit and having good adhesive strength after heating. "In the copper foil for forming the copper layer on the surface of the polyimide resin layer, the copper foil is in a state where the cobalt layer or the cobalt layer and the nickel-zinc alloy layer are laminated on the adhesive surface with the polyimide resin layer. A surface-treated copper foil for producing a flexible copper-clad laminate, which is characterized by comprising any one of the surface-treated layers, is disclosed, and is intended for a non-roughened surface-treated copper foil. In paragraph 0034 of the specification of Patent Document 1, “Furthermore, it is preferable that the surface of the surface-treated copper foil to be bonded to the polyimide resin substrate has a gloss [Gs (60 °)] of 70 or more. This is to ensure good fine-pitch circuit forming ability and good optical transparency required for optical automatic inspection (AOI inspection), for example ... (omitted) ... In the present invention, gloss The degree [Gs (60 °)] is 70 or more. However, when the gloss is less than 70, good fine pitch circuit forming ability cannot be obtained, and it is obtained at the time of inspection by an optical automatic inspection apparatus (AOI apparatus). It is difficult to ensure good light transmission. "
また、特許文献２に開示されているプラズマディスプレイパネルのブラックマスク形成に用いる銅箔を使用することも考えられる。このような用途の銅箔は、銅箔の接着面の色調が出来る限り黒色に近いものを使用するからである。この特許文献２には、プラズマディスプレイパネルの電磁波遮蔽に用いる導電性メッシュの製造に用いる銅箔が開示されており、特許文献２に開示の黒色化表面処理銅箔の表面は、ブラックマスク形成の要求に応えるニッケル系黒色化処理面又はコバルト系黒色化処理面である。この特許文献２に開示の銅箔を用いてフレキシブルプリント配線板を製造すると、フレキシブルプリント配線板の銅箔を除去して露出した樹脂フィルムの曇り度（Ｈａｚｅ）が低く、光透過性に優れ、フレキシブルプリント配線板のＡＯＩにおいて要求される色調の差も十分に満足できると考えられる。 It is also conceivable to use a copper foil used for forming a black mask of a plasma display panel disclosed in Patent Document 2. This is because the copper foil for such use uses a copper foil with a color tone as close to black as possible. This Patent Document 2 discloses a copper foil used for manufacturing a conductive mesh used for shielding electromagnetic waves of a plasma display panel, and the surface of the blackened surface-treated copper foil disclosed in Patent Document 2 is formed by black mask formation. It is a nickel-based blackening surface or a cobalt-based blackening surface that meets the requirements. When a flexible printed wiring board is manufactured using the copper foil disclosed in Patent Document 2, the haze (Haze) of the resin film exposed by removing the copper foil of the flexible printed wiring board is low, and the light transmittance is excellent. It is considered that the difference in color tone required in the AOI of the flexible printed wiring board can be sufficiently satisfied.
しかしながら、特許文献１に開示のフレキシブル銅張積層板製造用の表面処理銅箔は、無粗化の表面処理銅箔であるため、フレキシブルプリント配線板の樹脂フィルムの表面を粗さない平坦性を備えるが、この表面処理銅箔の接着面が過剰に平坦であると、表面処理銅箔と樹脂フィルムとの接着の際に、その接着界面にシワや気泡が生じやすくなる。従って、フレキシブル銅張積層板に使用する表面処理銅箔には、当該シワや気泡が生じにくい適度な粗さを備え、且つ、平坦な接着面を備えることが求められている。 However, since the surface-treated copper foil for manufacturing a flexible copper-clad laminate disclosed in Patent Document 1 is a non-roughened surface-treated copper foil, it has flatness that does not roughen the surface of the resin film of the flexible printed wiring board. However, when the bonding surface of the surface-treated copper foil is excessively flat, wrinkles and bubbles are likely to occur at the bonding interface when the surface-treated copper foil and the resin film are bonded. Therefore, the surface-treated copper foil used for the flexible copper-clad laminate is required to have an appropriate roughness that is unlikely to cause wrinkles and bubbles and a flat adhesive surface.
また、特許文献２に開示の黒色化表面処理銅箔の黒色化表面を、フレキシブル銅張積層板の製造に用いても、上述と同様に、表面処理銅箔と樹脂フィルムとの接着の際に、接着界面にシワや気泡が生じやすくなる。更に、特許文献２に開示の黒色化表面処理銅箔の黒色化表面は、ニッケル系黒色化処理面又はコバルト系黒色化処理面であり、銅エッチング液によるエッチングが困難となる傾向がある。従って、回路形成の際には、銅エッチング液によるオーバーエッチングの時間が長くなるため、銅部分のエッチングが過剰となり、エッチングファクターに優れたファインピッチ回路の形成が困難となる。また、十分なオーバーエッチングの時間を設けたつもりでも、回路間にニッケル又はコバルトが残留し、マイグレーションの発生確率が高くなり、製品の信頼性が低下するため好ましくない。 Further, even when the blackened surface of the blackened surface-treated copper foil disclosed in Patent Document 2 is used for the production of a flexible copper-clad laminate, the surface-treated copper foil and the resin film are bonded together in the same manner as described above. Wrinkles and bubbles are likely to occur at the bonding interface. Furthermore, the blackened surface of the blackened surface-treated copper foil disclosed in Patent Document 2 is a nickel-based blackened surface or a cobalt-based blackened surface, and etching with a copper etchant tends to be difficult. Accordingly, when the circuit is formed, the time for overetching with the copper etching solution becomes long, so that the copper portion is excessively etched, and it becomes difficult to form a fine pitch circuit having an excellent etching factor. Even if a sufficient over-etching time is provided, nickel or cobalt remains between the circuits, the probability of migration increases, and the reliability of the product decreases, which is not preferable.
これらのことから、本件出願は、特許文献２に開示されている銅箔と同等のＣＣＤ視認性及びＡＯＩの検出精度を向上させることの可能な黒色化表面を備え、フレキシブルプリント配線板製造に適した適度な粗さを備え、且つ、良好なエッチング特性を備えるプリント配線板用銅箔の提供を目的とする。 For these reasons, the present application has a blackened surface capable of improving CCD visibility and AOI detection accuracy equivalent to the copper foil disclosed in Patent Document 2, and is suitable for flexible printed wiring board production. Another object of the present invention is to provide a copper foil for a printed wiring board having an appropriate roughness and good etching characteristics.
そこで、本件発明者等は、以下の黒色化表面処理銅箔をフレキシブルプリント配線板製造に用いることで、上述の課題を解決することに想到した。 Therefore, the present inventors have conceived of solving the above-mentioned problems by using the following blackened surface-treated copper foil for manufacturing a flexible printed wiring board.
黒色化表面処理銅箔： 本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔は、樹脂フィルムに積層するための黒色粗化面（以下、単に「黒色粗化面」と称する。）を備える表面処理銅箔であり、当該黒色粗化面は、うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下であり、且つ、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０以下の色調を備えることを特徴とする。 Blackened surface-treated copper foil: The blackened surface-treated copper foil for producing a flexible printed wiring board according to the present application is referred to as a black roughened surface (hereinafter simply referred to as “black roughened surface”) for laminating on a resin film. And the black roughened surface has a maximum waviness difference (Wmax) of 1.2 μm or less, and a lightness L * of the L * a * b * color system of 30. The following color tone is provided.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の前記黒色粗化面は、粒径１０ｎｍ〜２５０ｎｍの銅粒子を付着させて粗化したものであることが好ましい。 It is preferable that the black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application is roughened by attaching copper particles having a particle size of 10 nm to 250 nm.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の前記黒色粗化面は、３μｍ×３μｍの領域において、４００個〜２５００個の銅粒子が付着していることが好ましい。 It is preferable that 400 to 2500 copper particles adhere to the black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application in an area of 3 μm × 3 μm.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の前記黒色粗化面は、平均粗さＲａが０．５μｍ以下であることが好ましい。 The black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application preferably has an average roughness Ra of 0.5 μm or less.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の前記黒色粗化面は、動摩擦係数が０．５０以上であることが好ましい。 The black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application preferably has a dynamic friction coefficient of 0.50 or more.
黒色化表面処理銅箔の製造方法： 本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造方法は、上述のフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造であって、銅箔のうねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下の表面に、銅濃度が１０ｇ／Ｌ〜２０ｇ／Ｌ、フリー硫酸濃度が１５ｇ／Ｌ〜１００ｇ／Ｌ、９−フェニルアクリジン濃度が１００ｍｇ／Ｌ〜２００ｍｇ／Ｌ、塩素濃度が２０ｍｇ／Ｌ〜１００ｍｇ／Ｌの黒色粗化用銅電解溶液を用いて微細銅粒子を付着させて黒色粗化を行うことを特徴とする。 Manufacturing method of black surface treatment copper foil: The manufacturing method of the black surface treatment copper foil for flexible printed wiring board manufacture which concerns on this application is manufacture of the blackening surface treatment copper foil for the above-mentioned flexible printed wiring board manufacture. The copper foil waviness (Wmax) is 1.2 μm or less on the surface, the copper concentration is 10 g / L to 20 g / L, the free sulfuric acid concentration is 15 g / L to 100 g / L, 9-phenylacridine The black roughening is performed by attaching fine copper particles using a black roughening copper electrolytic solution having a concentration of 100 mg / L to 200 mg / L and a chlorine concentration of 20 mg / L to 100 mg / L.
フレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造方法において、溶液温度２０℃〜４０℃の黒色粗化用銅電解溶液中で、銅箔を陰極に分極し、電流密度３０Ａ／ｄｍ２〜１００Ａ／ｄｍ２で電解することにより、銅箔表面への微細銅粒子の付着形成を行うことが好ましい。In the method for producing a blackened surface-treated copper foil for producing a flexible printed wiring board, the copper foil is polarized to the cathode in a black roughening copper electrolytic solution having a solution temperature of 20 ° C. to 40 ° C., and a current density of 30 A / dm 2. It is preferable to perform adhesion formation of fine copper particles on the surface of the copper foil by electrolysis at ˜100 A / dm 2 .
銅張積層板： 本件出願に係るフレキシブルプリント配線板製造用の銅張積層板は、上述のフレキシブルプリント配線板製造用の黒色化表面処理銅箔を用いて得られることを特徴とする。 Copper-clad laminate: A copper-clad laminate for producing a flexible printed wiring board according to the present application is obtained using the above-described blackened surface-treated copper foil for producing a flexible printed wiring board.
フレキシブルプリント配線板： 本件出願に係るフレキシブルプリント配線板は、上述のフレキシブルプリント配線板製造用の銅張積層板を用いて得られることを特徴とする。 Flexible printed wiring board: The flexible printed wiring board according to the present application is obtained by using the above-described copper-clad laminate for manufacturing a flexible printed wiring board.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔は、ＣＣＤ視認性及びＡＯＩの検査精度に優れる黒色化表面を備える。また、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔は、微細な粗化粒子が銅で形成されているため、良好なエッチング特性を備えている。従って、回路形成時のエッチングにおけるオーバーエッチングの時間を短縮化することが可能であり、極めて良好なエッチングファクターを備えるファインピッチ回路の形成を可能にする。 The blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has a blackened surface excellent in CCD visibility and AOI inspection accuracy. Further, the blackened surface-treated copper foil for producing a flexible printed wiring board according to the present application has good etching characteristics because fine roughened particles are formed of copper. Therefore, it is possible to shorten the over-etching time in etching at the time of circuit formation, and it is possible to form a fine pitch circuit having a very good etching factor.
以下、本件出願に係る「黒色化表面処理銅箔」、「黒色化表面処理銅箔の製造方法」、「銅張積層板」、「フレキシブルプリント配線板」の各形態に関して説明する。 Hereinafter, each form of “blackened surface-treated copper foil”, “manufacturing method of blackened surface-treated copper foil”, “copper-clad laminate”, and “flexible printed wiring board” according to the present application will be described.
黒色化表面処理銅箔： 本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔は、うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下であり、且つ、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０以下の色調の黒色粗化面を備えることを特徴とする。Blackened surface-treated copper foil: The blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has a maximum waviness difference (Wmax) of 1.2 μm or less, and L * a * b *. It is characterized by having a black roughened surface having a color tone having a lightness L * of 30 or less.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の黒色粗化面は、うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下であることが１つの特徴である。この「うねりの最大高低差（Ｗｍａｘ）」とは、三次元表面構造解析顕微鏡を用いて得られる試料表面の凹凸に関する情報から、うねりに係る波形データをフィルタリングして抽出した波形データにおける高低差の最大値（波形の最大ピーク高さと最大バレー深さの和）をいう。このうねりの最大高低差（Ｗｍａｘ）が１．２μｍを超える黒色粗化面を備える表面処理銅箔を用いてフレキシブルプリント配線板を製造した場合、フレキシブルプリント配線板の銅箔をエッチング除去して露出した樹脂フィルムの曇り度（Ｈａｚｅ）が高くなり、ＣＣＤ視認性及びＡＯＩの検査精度が低下する。そして、この曇り度（Ｈａｚｅ）を安定して低い値にするためには、うねりの最大高低差（Ｗｍａｘ）が１．０μｍ以下とすることがより好ましい。 One characteristic of the black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application is that the maximum height difference (Wmax) of the waviness is 1.2 μm or less. This “maximum undulation height difference (Wmax)” refers to the difference in height in the waveform data extracted by filtering the waveform data relating to undulation from the information on the unevenness of the sample surface obtained using a three-dimensional surface structure analysis microscope. The maximum value (the sum of the maximum peak height of the waveform and the maximum valley depth). When a flexible printed wiring board is manufactured using a surface-treated copper foil having a black roughened surface with a maximum height difference (Wmax) of this undulation exceeding 1.2 μm, the copper foil of the flexible printed wiring board is removed by etching. The haze (Haze) of the resin film is increased, and the CCD visibility and AOI inspection accuracy are reduced. And in order to make this haze degree (Haze) into a low value stably, it is more preferable that the maximum height difference (Wmax) of a wave | undulation shall be 1.0 micrometer or less.
そして、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔は、当該黒色粗化面が、ＪＩＳ Ｚ８７２９に定めるＬ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０以下の色調を備えることも特徴である。Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０を超えると、粗化粒子の粒径が大きくなり、フレキシブルプリント配線板の銅箔をエッチング除去して露出した樹脂フィルムの曇り度（Ｈａｚｅ）が高くなる。また、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０を超えると、この黒色化表面処理銅箔を用いて形成した回路背面の色調と、樹脂フィルムとの色調のコントラストが低下するため、ＣＣＤ視認性が低下し、ＡＯＩの検査精度も低下する傾向となる。そして、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が２０以下であると、当該樹脂フィルムの曇り度（Ｈａｚｅ）が安定して低下する。また、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が１５以下であると、当該樹脂フィルムの曇り度（Ｈａｚｅ）と共に、回路背面の色調と樹脂フィルムとの色調のコントラストも明瞭化してＣＣＤ視認性がさらに向上する。And the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has a color tone whose L * a * b * color system lightness L * is 30 or less as defined in JIS Z8729. It is also characterized by comprising. When the lightness L * of the L * a * b * color system exceeds 30, the particle size of the roughened particles increases, and the haze (Haze) of the resin film exposed by etching away the copper foil of the flexible printed wiring board is removed. ) Becomes higher. In addition, if the lightness L * of the L * a * b * color system exceeds 30, the contrast between the color tone of the back surface of the circuit formed using this blackened surface-treated copper foil and the color tone of the resin film decreases. CCD visibility decreases, and AOI inspection accuracy tends to decrease. When the lightness L * of the L * a * b * color system is 20 or less, the haze (Haze) of the resin film is stably reduced. If the lightness L * of the L * a * b * color system is 15 or less, the haze of the resin film (Haze) and the contrast between the color tone of the back of the circuit and the color tone of the resin film are clarified. Visibility is further improved.
本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の黒色粗化面は、粒径１０ｎｍ〜２５０ｎｍの銅粒子を付着させたものであることが好ましい。ここで、当該銅粒子の粒径の下限値を１０ｎｍとしている。しかし、１０ｎｍ未満の粒径の粗化粒子を積極的に排除する意味ではないが、粗化粒子が微細になりすぎると、樹脂フィルムに対するアンカー効果が低下する可能性がある。一方、当該粗化粒子の粒径が２５０ｎｍを超えると、表面処理銅箔を用いて製造した銅張積層板の銅箔をエッチング除去して露出した樹脂フィルム部の曇り度（Ｈａｚｅ）が高くなり、ＣＣＤ視認性及びＡＯＩの検査精度も低下するため好ましくない。なお、銅粒子の形状には、特段の限定はないが、銅粒子が略球状であることが好ましい。銅粒子が略球状であれば粉落ちを防止できるからである。 It is preferable that the black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has copper particles having a particle size of 10 nm to 250 nm attached thereto. Here, the lower limit of the particle size of the copper particles is 10 nm. However, this does not mean that the coarse particles having a particle diameter of less than 10 nm are positively excluded, but if the coarse particles become too fine, the anchor effect on the resin film may be lowered. On the other hand, when the particle size of the roughened particles exceeds 250 nm, the haze of the resin film portion exposed by etching and removing the copper foil of the copper clad laminate produced using the surface-treated copper foil increases. In addition, CCD visibility and AOI inspection accuracy are also lowered, which is not preferable. In addition, although there is no special limitation in the shape of a copper particle, it is preferable that a copper particle is a substantially spherical shape. This is because if the copper particles are substantially spherical, powder falling can be prevented.
また、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の黒色粗化面は、３μｍ×３μｍの領域において、４００個〜２５００個の銅粒子が付着していることが好ましい。この所定の領域内における銅粒子の付着個数が４００個未満の場合には、上述のＬ＊ａ＊ｂ＊表色系の明度Ｌ＊ を３０以下とすることが困難となり好ましくない。一方、所定の領域内における銅粒子の付着個数が２５００個を超える場合には、付着した銅粒子の脱落が起こり易くなり、且つ、上述の曇り度（Ｈａｚｅ）の値が高くなる傾向があり、ＣＣＤ視認性及びＡＯＩの検査精度が低下するため好ましくない。Moreover, it is preferable that 400-2500 copper particles have adhered to the black roughening surface of the blackening surface treatment copper foil for flexible printed wiring board manufacture which concerns on this application in the area | region of 3 micrometers x 3 micrometers. If the number of adhered copper particles in this predetermined region is less than 400, it is not preferable because the lightness L * of the above-mentioned L * a * b * color system is difficult to be 30 or less. On the other hand, when the number of adhered copper particles in a predetermined region exceeds 2500, the attached copper particles are likely to fall off, and the haze value tends to increase. This is not preferable because CCD visibility and AOI inspection accuracy are lowered.
以上に述べてきた本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の黒色粗化面を構成する銅粒子は、銅と不可避不純物とからなり、エッチングを阻害する合金成分等を含まないことが好ましい。銅粒子が銅箔を構成する銅成分と同等の組成であれば、銅エッチング液でのエッチング速度が銅箔と銅粒子とで同等であるため、エッチングによる回路形成条件の工程設計が容易となる。 The copper particles constituting the black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application described above are composed of copper and inevitable impurities, and include alloy components that inhibit etching. It is preferably not included. If the copper particles have the same composition as the copper component constituting the copper foil, the etching rate in the copper etching solution is the same for the copper foil and the copper particles, so that the process design of circuit formation conditions by etching becomes easy. .
そして、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の黒色粗化面は、触針式表面粗さ計を用いて測定したときの平均粗さＲａが０．５μｍ以下であることが好ましい。本件出願に係る黒色化表面処理銅箔は、平均粗さに関しても、極めて低い値を備えている。この平均粗さＲａが０．５μｍを超えると、回路形成するエッチング工程において、配線間の樹脂フィルム内に進入した粗化粒子がエッチング残として残留しないよう設けるオーバーエッチングの時間が長くなるため、配線のサイドウォールを必要以上に溶解することになり、良好なエッチングファクターを備えるファインピッチ回路の形成が困難となるため好ましくない。また、当該平均粗さＲａが０．３μｍ以下であることがより好ましい。良好なエッチングファクターを備えるファインピッチ回路の形成と、同時に表面処理銅箔の黒色粗化面と樹脂フィルムとの積層界面に対する溶液の浸食を防止して耐薬品性能を向上させることができるからである。 And as for the black roughening surface of the blackening surface treatment copper foil for flexible printed wiring board manufacture which concerns on this application, average roughness Ra when measured using a stylus type surface roughness meter is 0.5 micrometer or less. Preferably there is. The blackened surface-treated copper foil according to the present application has an extremely low value with respect to the average roughness. If this average roughness Ra exceeds 0.5 μm, in the etching process for forming the circuit, the overetching time provided so that the roughened particles that have entered the resin film between the wirings do not remain as etching residues will become long. This is not preferable because the side wall is dissolved more than necessary, and it becomes difficult to form a fine pitch circuit having a good etching factor. Further, the average roughness Ra is more preferably 0.3 μm or less. This is because it is possible to improve the chemical resistance performance by forming a fine pitch circuit with a good etching factor and at the same time preventing erosion of the solution to the laminated interface between the black roughened surface of the surface-treated copper foil and the resin film. .
更に、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の黒色粗化面は、動摩擦係数が０．５０以上であることが好ましい。この動摩擦係数が０．５０未満の場合には、ロールラミネート法で樹脂フィルムと黒色化表面処理銅箔とを積層する際に、黒色化表面処理銅箔の黒色粗化面が平滑過ぎて、黒色化表面処理銅箔と樹脂フィルムとの接着界面で滑りが生じ、シワが発生しやすくなるため良好な積層がしにくくなる。また、この動摩擦係数が０．５０未満の場合には、黒色化表面処理銅箔と樹脂フィルムとの接着界面に気泡が生じやすくなる傾向もある。 Furthermore, it is preferable that the black roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has a dynamic friction coefficient of 0.50 or more. When this dynamic friction coefficient is less than 0.50, the black roughened surface of the blackened surface-treated copper foil is too smooth when the resin film and the blackened surface-treated copper foil are laminated by the roll laminating method. Sliding occurs at the adhesive interface between the surface-treated copper foil and the resin film, and wrinkles are likely to occur, making it difficult to achieve good lamination. Moreover, when this dynamic friction coefficient is less than 0.50, there also exists a tendency for air bubbles to be easily generated at the adhesion interface between the blackened surface-treated copper foil and the resin film.
なお、以上に述べてきた黒色化表面処理銅箔は、厚さに関しては、特段の限定は無い。また、通常の銅箔の表面に黒色粗化を行ったものに限らず、キャリア箔付銅箔の銅箔表面の黒色粗化を行ったものも含む概念であることを明記しておく。 The blackened surface-treated copper foil described above is not particularly limited with respect to the thickness. In addition, it is clearly stated that the concept includes not only the surface of the normal copper foil subjected to black roughening but also the surface of the copper foil with carrier foil subjected to black roughening.
黒色化表面処理銅箔の製造方法： 本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造方法は、上述のフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造であって、銅箔のうねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下の表面に、微細銅粒子を付着させて黒色粗化を行う。この樹脂フィルムに対する接着面のうねりの最大高低差（Ｗｍａｘ）が１．２μｍを超えると、黒色粗化後において、うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下となりにくい。そして、この黒色化表面処理銅箔の製造方法における工程のバラツキ等を考慮し、黒色粗化後のうねりの最大高低差（Ｗｍａｘ）を安定して１．２μｍ以下とするためには、うねりの最大高低差（Ｗｍａｘ）が０．８μｍ以下にすることがより好ましい。 Manufacturing method of black surface treatment copper foil: The manufacturing method of the black surface treatment copper foil for flexible printed wiring board manufacture which concerns on this application is manufacture of the blackening surface treatment copper foil for the above-mentioned flexible printed wiring board manufacture. Then, black roughening is performed by attaching fine copper particles to the surface where the maximum height difference (Wmax) of the undulation of the copper foil is 1.2 μm or less. When the maximum height difference (Wmax) of the waviness of the adhesive surface with respect to the resin film exceeds 1.2 μm, the maximum height difference (Wmax) of the waviness is less likely to be 1.2 μm or less after black roughening. In consideration of variations in the process in the method for producing the blackened surface-treated copper foil, the maximum height difference (Wmax) of the waviness after the roughening of black is stably reduced to 1.2 μm or less. The maximum height difference (Wmax) is more preferably 0.8 μm or less.
以上に述べた黒色化表面処理銅箔の製造方法で使用する黒色粗化前の銅箔として、電解銅箔及び圧延銅箔の双方の使用が可能である。また、うねりの最大高低差（Ｗｍａｘ）が１．２μｍを超える銅箔であっても、このような銅箔表面に対して、エッチング処理や、銅めっき処理等を行うことにより、うねりの最大高低差（Ｗｍａｘ）を１．２μｍ以下としてもよい。そして、ここでいう銅箔は、樹脂フィルムに対する接着面のうねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下という条件を満足する限り、無粗化の銅箔であっても、予備的粗化を施したものであってもよい。また、銅箔の厚さに関しても、特段の限定は無い。 Both the electrolytic copper foil and the rolled copper foil can be used as the copper foil before black roughening used in the method for producing the blackened surface-treated copper foil described above. Moreover, even if it is a copper foil in which the maximum height difference (Wmax) of the undulation exceeds 1.2 μm, the maximum undulation of the undulation can be obtained by performing etching treatment, copper plating treatment, etc. on such a copper foil surface. The difference (Wmax) may be 1.2 μm or less. And as long as the copper foil as used herein satisfies the condition that the maximum height difference (Wmax) of the swell of the adhesive surface to the resin film satisfies 1.2 μm or less, even if it is a non-roughened copper foil, preliminary roughening It may be given. Moreover, there is no special limitation regarding the thickness of copper foil.
当該銅箔のうねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下の表面に、微細銅粒子を付着させて黒色粗化を行うにあたり、以下の黒色粗化用銅電解溶液を用いることが好ましい。即ち、銅濃度が１０ｇ／Ｌ〜２０ｇ／Ｌ、フリー硫酸濃度が１５ｇ／Ｌ〜１００ｇ／Ｌ、９−フェニルアクリジン濃度が１００ｍｇ／Ｌ〜２００ｍｇ／Ｌ、塩素濃度が２０ｍｇ／Ｌ〜１００ｍｇ／Ｌの黒色粗化用銅電解溶液を用いる。この黒色粗化用銅電解溶液は、銅濃度が１０ｇ／Ｌ〜２０ｇ／Ｌ、フリー硫酸濃度が１５ｇ／Ｌ〜１００ｇ／Ｌの硫酸酸性銅電解液を基本溶液として用いる。ここで、当該銅濃度が１０ｇ／Ｌ未満の場合には、銅粒子の電着速度が遅くなり、工業的に要求される生産性を満足しないため好ましくない。一方、当該銅濃度が２０ｇ／Ｌを超えると、後述する電流密度との関係で、平滑めっき条件に近づき、黒色粗化が困難となるため好ましくない。そして、フリー硫酸濃度は、この銅濃度との関係で、この濃度範囲を逸脱すると、電解時の通電特性が変化して、良好な黒色粗化が困難となるため好ましくない。 In performing black roughening by attaching fine copper particles to a surface having a maximum height difference (Wmax) of undulation of the copper foil of 1.2 μm or less, it is preferable to use the following black roughening copper electrolytic solution. That is, the copper concentration is 10 g / L to 20 g / L, the free sulfuric acid concentration is 15 g / L to 100 g / L, the 9-phenylacridine concentration is 100 mg / L to 200 mg / L, and the chlorine concentration is 20 mg / L to 100 mg / L. A black roughening copper electrolytic solution is used. This black roughening copper electrolytic solution uses a sulfuric acid acidic copper electrolytic solution having a copper concentration of 10 g / L to 20 g / L and a free sulfuric acid concentration of 15 g / L to 100 g / L as a basic solution. Here, when the copper concentration is less than 10 g / L, the electrodeposition rate of the copper particles is slow, and the industrially required productivity is not satisfied, which is not preferable. On the other hand, if the copper concentration exceeds 20 g / L, it is not preferable because it approaches smooth plating conditions and makes it difficult to roughen the black in relation to the current density described later. If the concentration of free sulfuric acid deviates from this concentration range due to the relationship with the copper concentration, the current-carrying characteristics during electrolysis change and it becomes difficult to achieve good black roughening.
そして、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造方法で用いる黒色粗化用銅電解溶液の場合、９−フェニルアクリジン濃度を１００ｍｇ／Ｌ〜２００ｍｇ／Ｌの範囲で含有することが好ましい。この９−フェニルアクリジンは、銅箔の表面に付着形成する銅粒子の粒径を微細化し、粒子形状の球状化を促進する添加剤として機能する。黒色粗化用銅電解溶液中の９−フェニルアクリジン濃度が１００ｍｇ／Ｌ未満の場合には、銅粒子の粒径の微細化効果が得られにくく、粒子形状の球状化の促進効果も低くなるため好ましくない。一方、黒色粗化用銅電解溶液中の９−フェニルアクリジン濃度が２００ｍｇ／Ｌを超えるものとしても、銅粒子の粒径の微細化効果、及び、粒子形状の球状化の促進効果も同時に飽和して添加量に比例した効果が得られず、単なる資源の無駄使いとなるため好ましくない。 And in the case of the black roughening copper electrolytic solution used with the manufacturing method of the blackening surface treatment copper foil for flexible printed wiring board manufacture which concerns on this application, 9-phenylacridine density | concentration is in the range of 100 mg / L-200 mg / L. It is preferable to contain. This 9-phenylacridine functions as an additive that refines the particle size of the copper particles deposited on the surface of the copper foil and promotes the spheroidization of the particle shape. When the 9-phenylacridine concentration in the black roughening copper electrolytic solution is less than 100 mg / L, the effect of reducing the particle size of the copper particles is difficult to obtain, and the effect of promoting the spheroidization of the particle shape is also reduced. It is not preferable. On the other hand, even when the concentration of 9-phenylacridine in the black roughening copper electrolytic solution exceeds 200 mg / L, the effect of refining the particle size of the copper particles and the effect of promoting the spheroidization of the particle shape are saturated at the same time. Therefore, an effect proportional to the added amount cannot be obtained, and this is not preferable because it is simply a waste of resources.
更に、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造方法で用いる黒色粗化用銅電解溶液の塩素濃度は、２０ｍｇ／Ｌ〜１００ｍｇ／Ｌの範囲で含有することが好ましい。当該黒色粗化用銅電解溶液の塩素濃度が２０ｍｇ／Ｌ未満の場合には、銅粒子を形成するためのヤケめっき状態とすることが困難となり、良好な形状の粗化粒子が得られなくなるため好ましくない。一方、当該黒色粗化用銅電解溶液の塩素濃度が１００ｍｇ／Ｌを超える場合には、黒色化表面処理銅箔の黒色粗化面の色調にバラツキが生じやすくなると同時に、粒子形状の球状化が良好に行われなくなるため好ましくない。 Furthermore, the chlorine concentration of the black roughening copper electrolytic solution used in the method for producing a blackened surface-treated copper foil for producing a flexible printed wiring board according to the present application may be contained in a range of 20 mg / L to 100 mg / L. preferable. When the chlorine concentration of the black roughening copper electrolytic solution is less than 20 mg / L, it is difficult to obtain a burned plating state for forming copper particles, and rough particles having a good shape cannot be obtained. It is not preferable. On the other hand, when the chlorine concentration of the black roughening copper electrolytic solution exceeds 100 mg / L, the color tone of the black roughened surface of the blackened surface-treated copper foil is likely to vary, and at the same time, the particle shape is spheroidized. This is not preferable because it is not performed well.
以上に述べてきた黒色粗化用銅電解溶液用いて、銅箔表面に黒色粗化を行う場合、溶液温度２０℃〜４０℃の銅電解液中で、銅箔を陰極に分極し、電流密度３０Ａ／ｄｍ２〜１００Ａ／ｄｍ２で電解することが好ましい。ここで、溶液温度は、２０℃〜４０℃の範囲であることが好ましい。この溶液温度が２０℃未満になると、形成する粗化粒子の形状にバラツキが生じやすくなるため好ましくない。一方、この溶液温度が４０℃を超えると、黒色粗化用銅電解溶液の溶液性状の変化が起こりやすく、安定したヤケめっきが出来なくなる傾向があるため好ましくない。When performing black roughening on the surface of the copper foil using the black roughening copper electrolytic solution described above, the copper foil is polarized to the cathode in the copper electrolyte at a solution temperature of 20 ° C. to 40 ° C., and the current density it is preferred to electrolysis at 30A / dm 2 ~100A / dm 2 . Here, the solution temperature is preferably in the range of 20 ° C to 40 ° C. When the solution temperature is less than 20 ° C., the shape of the coarse particles to be formed tends to vary, which is not preferable. On the other hand, when the solution temperature exceeds 40 ° C., the solution property of the black roughening copper electrolytic solution is likely to change, and there is a tendency that stable burn-out plating cannot be performed.
そして、銅電解液中で、銅箔を陰極に分極して黒色粗化を行うときの電流密度は、３０Ａ／ｄｍ２〜１００Ａ／ｄｍ２の範囲であることが好ましい。この電流密度が、３０Ａ／ｄｍ２未満の場合には、十分な黒色粗化が出来ず、黒色粗化面の明度Ｌ＊ を３０以下とすることが困難となるため好ましくない。一方、電流密度が１００Ａ／ｄｍ２を超えると、微細な銅粒子の析出速度が過剰となり、形成される銅粒子形状が、良好な球状体とならなくなるため好ましくない。Then, a copper electrolyte solution, current density when performing black roughening polarized copper foil on the cathode is preferably in a range of 30A / dm 2 ~100A / dm 2 . When the current density is less than 30 A / dm 2 , it is not preferable because sufficient black roughening cannot be performed and it becomes difficult to set the lightness L * of the black roughened surface to 30 or less. On the other hand, when the current density exceeds 100 A / dm 2 , the precipitation rate of fine copper particles becomes excessive, and the shape of the formed copper particles does not become a good spherical body, which is not preferable.
銅張積層板： 本件出願に係る銅張積層板は、上述のフレキシブルプリント配線板製造用の黒色化表面処理銅箔と樹脂フィルムとを積層して得られることを特徴とするフレキシブル銅張積層板である。このときの樹脂フィルムとして、ポリイミド樹脂フィルム、ＰＥＴフィルム、アラミド樹脂フィルム等の使用が可能であるが、フレキシブルプリント配線板の樹脂フィルムとして使用できる限り、特段の限定は無い。また、フレキシブル銅張積層板の製造は、通常の積層方式、連続ラミネート方式、キャスティング方式等を採用し、黒色化表面処理銅箔の表面に樹脂層を形成することができる。ここでいうキャスティング方式とは、本件発明に係る黒色化表面処理銅箔の表面に、ポリアミド酸等の加熱によりポリイミド樹脂化する樹脂組成膜を形成し、加熱して縮合反応を起こさせて、黒色化表面処理銅箔の表面にポリイミド樹脂フィルム層を直接形成する方法である。 Copper-clad laminate: A copper-clad laminate according to the present application is obtained by laminating a blackened surface-treated copper foil and a resin film for manufacturing the above-mentioned flexible printed wiring board. It is. A polyimide resin film, a PET film, an aramid resin film, or the like can be used as the resin film at this time, but there is no particular limitation as long as it can be used as a resin film for a flexible printed wiring board. Moreover, the manufacture of a flexible copper clad laminated board employ | adopts a normal lamination system, a continuous lamination system, a casting system, etc., and can form a resin layer on the surface of blackening surface treatment copper foil. As used herein, the casting method refers to the formation of a resin composition film that is converted to a polyimide resin by heating, such as polyamic acid, on the surface of the blackened surface-treated copper foil according to the present invention. In this method, a polyimide resin film layer is directly formed on the surface of the surface-treated copper foil.
フレキシブルプリント配線板： このフレキシブルプリント配線板は、上述の銅張積層板の状態から、本件出願に係る黒色化表面処理銅箔をエッチング加工すると、当該黒色化表面処理銅箔の溶解した部分に露出する樹脂フィルムの曇り度（Ｈａｚｅ）を大幅に低下させることができる。この曇り度（Ｈａｚｅ）の値は、樹脂フィルムの種類によっても異なる。しかし、銅張積層板に使用する樹脂フィルムが同一である限り、本件出願に係る黒色化表面処理銅箔を用いることで、従来の表面処理銅箔を用いた場合に比べ、極めて低い曇り度（Ｈａｚｅ）を得ることが可能となり、ＣＣＤ視認性及びＡＯＩに対する適合性が飛躍的に高まる。 Flexible printed wiring board: This flexible printed wiring board is exposed to the melted portion of the blackened surface-treated copper foil when the blackened surface-treated copper foil according to the present application is etched from the state of the above-described copper-clad laminate. The haze (Haze) of the resin film to be reduced can be greatly reduced. The haze value varies depending on the type of resin film. However, as long as the resin film used for the copper-clad laminate is the same, by using the blackened surface-treated copper foil according to the present application, extremely low haze (when using the conventional surface-treated copper foil) ( Haze) can be obtained, and the CCD visibility and compatibility with AOI are remarkably increased.
実施例１では、厚さ１２μｍの電解銅箔を製造し、黒色粗化と、防錆処理と、シランカップリング剤処理とを行って黒色化表面処理銅箔を作製し、後述する比較例との対比を行った。 In Example 1, an electrolytic copper foil having a thickness of 12 μm was produced, and blackened surface-treated copper foil was produced by performing blackening, rust prevention treatment, and silane coupling agent treatment. Contrast was performed.
電解銅箔の製造： 銅電解液に、以下に示す組成の硫酸酸性硫酸銅溶液を用い、陰極に表面粗さがＲａ＝０．２０μｍのチタン製の回転電極を用い、陽極にはＤＳＡを用いて、溶液温度４５℃、電流密度５５Ａ／ｄｍ２で電解し、厚さ１２μｍの電解銅箔を得た。この電解銅箔の析出面のうねりの最大高低差（Ｗｍａｘ）が０．８μｍであった。Production of electrolytic copper foil: An acidic copper sulfate solution having the following composition was used as the copper electrolyte, a titanium rotating electrode with a surface roughness Ra = 0.20 μm was used as the cathode, and DSA was used as the anode. Electrolysis was performed at a solution temperature of 45 ° C. and a current density of 55 A / dm 2 to obtain an electrolytic copper foil having a thickness of 12 μm. The maximum height difference (Wmax) of the undulation of the deposited surface of this electrolytic copper foil was 0.8 μm.
銅濃度： ８０ｇ／Ｌ
フリー硫酸濃度： １４０ｇ／Ｌ
ビス（３−スルホプロピル）ジスルフィド濃度： ３０ｍｇ／Ｌ
ジアリルジメチルアンモニウムクロライド重合体濃度： ５０ｍｇ／Ｌ
塩素濃度： ４０ｍｇ／ＬCopper concentration: 80 g / L
Free sulfuric acid concentration: 140 g / L
Bis (3-sulfopropyl) disulfide concentration: 30 mg / L
Diallyldimethylammonium chloride polymer concentration: 50 mg / L
Chlorine concentration: 40mg / L
黒色粗化： 上述の電解銅箔が備える電極面及び析出面の内、析出面側に対して、以下に示す組成の黒色粗化用銅電解溶液を用い、溶液温度３０℃、電流密度５０Ａ／ｄｍ２の条件で電解して、黒色粗化を行った。Black roughening: A black roughening copper electrolytic solution having the following composition is used for the deposition surface side of the electrode surface and the deposition surface included in the above-described electrolytic copper foil, a solution temperature of 30 ° C., and a current density of 50 A / Electrolysis was performed under the condition of dm 2 to perform black roughening.
銅濃度： １３ｇ／Ｌ
フリー硫酸濃度： ５５ｇ／Ｌ
９−フェニルアクリジン濃度： １４０ｍｇ／Ｌ
塩素濃度： ３５ｍｇ／ＬCopper concentration: 13g / L
Free sulfuric acid concentration: 55 g / L
9-phenylacridine concentration: 140 mg / L
Chlorine concentration: 35mg / L
防錆処理： 上述の黒色粗化が終了すると、当該黒色粗化後の電解銅箔の両面に防錆処理を行った。ここでは以下に述べる条件の無機防錆を採用した。ピロリン酸浴を用い、ピロリン酸カリウム濃度８０ｇ／Ｌ、亜鉛濃度０．２ｇ／Ｌ、ニッケル濃度２ｇ／Ｌ、液温４０℃、電流密度０．５Ａ／ｄｍ２で亜鉛−ニッケル合金防錆処理を行った。Rust prevention treatment: When the black roughening described above was completed, a rust prevention treatment was performed on both surfaces of the electrolytic copper foil after the black roughening. Here, inorganic rust prevention under the conditions described below was adopted. Using a pyrophosphate bath, zinc-nickel alloy rust prevention treatment is performed at a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, a liquid temperature of 40 ° C., and a current density of 0.5 A / dm 2. went.
そして、防錆処理として、亜鉛−ニッケル合金防錆処理の上に、更にクロメート層を形成した。このときのクロメート処理条件は、クロム酸濃度が１ｇ／Ｌ、ｐＨ１１、溶液温度２５℃、電流密度１Ａ／ｄｍ２で行った。And as a rust prevention process, the chromate layer was further formed on the zinc-nickel alloy rust prevention process. The chromate treatment was performed at a chromate concentration of 1 g / L, pH 11, a solution temperature of 25 ° C., and a current density of 1 A / dm 2 .
シランカップリング剤処理： 以上の防錆処理が完了すると水洗後、直ちにシランカップリング剤処理を行い、黒色粗化面の防錆処理層の上にシランカップリング剤の吸着を行った。このときの溶液は、純水を溶媒として、３−アミノプロピルトリメトキシシラン濃度を３ｇ／Ｌとしたものを用いた。そして、この溶液をシャワーリングにて、黒色粗化面に吹き付けて吸着処理した。シランカップリング剤の吸着が終了すると、最終的に電熱器により水分を気散させ、１２μｍ厚さの黒色化表面処理銅箔を得た。 Silane coupling agent treatment: When the above rust prevention treatment was completed, the silane coupling agent treatment was performed immediately after washing with water, and the silane coupling agent was adsorbed onto the rust prevention treatment layer on the black roughened surface. As the solution at this time, pure water was used as a solvent, and a 3-aminopropyltrimethoxysilane concentration of 3 g / L was used. Then, this solution was sprayed onto the black roughened surface by showering to be adsorbed. When the adsorption of the silane coupling agent was completed, water was finally diffused by an electric heater to obtain a blackened surface-treated copper foil having a thickness of 12 μm.
以上のようにして得られた本件出願に係る黒色化表面処理銅箔の走査型電子顕微鏡観察像を図１に示す。また、評価した諸特性に関しては、比較例との対比が容易となるよう表１に示す。 A scanning electron microscope observation image of the blackened surface-treated copper foil according to the present application obtained as described above is shown in FIG. The evaluated characteristics are shown in Table 1 so as to facilitate comparison with the comparative example.
実施例２では、厚さ１２μｍの電解銅箔を製造し、実施例１と同様の黒色粗化と、防錆処理と、シランカップリング剤処理とを行って黒色化表面処理銅箔を作製した。 In Example 2, an electrolytic copper foil having a thickness of 12 μm was manufactured, and the blackened surface-treated copper foil was produced by performing the same black roughening, rust prevention treatment, and silane coupling agent treatment as in Example 1. .
電解銅箔の製造： 銅電解液として、実施例１のビス（３−スルホプロピル）ジスルフィド濃度を２０ｍｇ／Ｌとした硫酸酸性硫酸銅溶液を用い、実施例１と同様の条件で、厚さ１２μｍの電解銅箔を得た。この電解銅箔の析出面のうねりの最大高低差（Ｗｍａｘ）が１．２μｍであった。 Production of electrolytic copper foil: As the copper electrolyte, a sulfuric acid copper sulfate solution in which the bis (3-sulfopropyl) disulfide concentration of Example 1 was 20 mg / L was used, and the thickness was 12 μm under the same conditions as in Example 1. An electrolytic copper foil was obtained. The maximum height difference (Wmax) of the undulation of the deposited surface of this electrolytic copper foil was 1.2 μm.
上述の電解銅箔を用い、実施例１と同様の黒色粗化、防錆処理、シランカップリング剤処理を行って、実施例２の黒色化表面処理銅箔を得た。評価した諸特性に関しては、比較例との対比が容易となるよう表１に示す。 The blackened surface-treated copper foil of Example 2 was obtained by performing the same black roughening, rust prevention treatment, and silane coupling agent treatment as in Example 1 using the above-described electrolytic copper foil. The evaluated characteristics are shown in Table 1 so as to facilitate comparison with the comparative example.
実施例３では、実施例１と同じ電解銅箔を用い、黒色粗化と、防錆処理と、シランカップリング剤処理とを行って黒色化表面処理銅箔を作製した。以下においては、実施例１と異なる黒色粗化に関してのみ述べる。 In Example 3, the same electrolytic copper foil as in Example 1 was used, and blackening, rust prevention treatment, and silane coupling agent treatment were performed to produce a blackened surface-treated copper foil. In the following, only black roughening different from that in Example 1 will be described.
黒色粗化： 上述の電解銅箔が備える電極面及び析出面の内、析出面側に対して、予備的粗化処理を施した。このときの予備的粗化処理は、以下の２段階のプロセスで行った。 Black roughening: A preliminary roughening treatment was performed on the deposition surface side of the electrode surface and the deposition surface included in the electrolytic copper foil. The preliminary roughening treatment at this time was performed by the following two-stage process.
予備的粗化処理の１段目は、銅濃度が１８ｇ／ｌ、フリー硫酸濃度が７０ｇ／ｌの粗化処理用銅電解溶液を用いて、溶液温度２５℃、電流密度４Ａ／ｄｍ２で、４秒間電解し、水洗した。そして、２段目は、銅濃度が６５ｇ／ｌ、フリー硫酸濃度が６０ｇ／ｌの銅電解溶液を用いて、溶液温度４５℃、電流密度５Ａ／ｄｍ２で、５秒間電解し、水洗して、予備的粗化処理を行った。この段階の電解銅箔の析出面は、うねりの最大高低差（Ｗｍａｘ）が０．９μｍであった。従って、予備的粗化処理前の当該析出面は、うねりの最大高低差（Ｗｍａｘ）が０．８μｍであり、当該うねりが大きく変動せず、適正な範囲のうねりであることが理解できる。The first stage of the preliminary roughening treatment uses a copper electrolytic solution for roughening treatment with a copper concentration of 18 g / l and a free sulfuric acid concentration of 70 g / l, at a solution temperature of 25 ° C. and a current density of 4 A / dm 2 . Electrolysis was performed for 4 seconds and washed with water. In the second stage, using a copper electrolytic solution having a copper concentration of 65 g / l and a free sulfuric acid concentration of 60 g / l, electrolysis is performed at a solution temperature of 45 ° C. and a current density of 5 A / dm 2 for 5 seconds, and washed with water. A preliminary roughening treatment was performed. The precipitation surface of the electrolytic copper foil at this stage had a maximum waviness difference (Wmax) of 0.9 μm. Therefore, it can be understood that the precipitation surface before the preliminary roughening treatment has a maximum waviness difference (Wmax) of 0.8 μm, and the waviness does not fluctuate greatly and is in an appropriate range.
そして、予備的粗化処理を施した当該析出面に、実施例１と同様にして、黒色粗化、防錆処理、シランカップリング剤処理を行って、実施例３の黒色化表面処理銅箔を得た。評価した諸特性に関しては、比較例との対比が容易となるよう表１に示す。 And the blackened surface-treated copper foil of Example 3 was performed to the said precipitation surface which performed the preliminary roughening process like Example 1 by carrying out black roughening, an antirust process, and a silane coupling agent process. Got. The evaluated characteristics are shown in Table 1 so as to facilitate comparison with the comparative example.
［比較例１］
比較例１は、実施例１で用いた電解銅箔の析出面に、実施例１と異なる方法で粗化処理を行った。よって、実施例１と粗化処理のみが異なるため、以下において粗化処理に関してのみ詳細に述べる。[Comparative Example 1]
In Comparative Example 1, the surface of the electrolytic copper foil used in Example 1 was roughened by a method different from Example 1. Therefore, since only the roughening process is different from the first embodiment, only the roughening process will be described in detail below.
粗化処理： 比較例１は、前記電解銅箔の析出面に対して、以下の２段階のプロセスで粗化処理を行った。粗化処理の１段目は、銅濃度が８ｇ／ｌ、フリー硫酸濃度が５０ｇ／ｌ、９−フェニルアクリジン濃度が１５０ｍｇ／ｌ、塩素濃度が５０ｍｇ／ｌの粗化処理用銅電解溶液を用いて、溶液温度３０℃、電流密度１９Ａ／ｄｍ２で電解し、水洗した。そして、２段目は、銅濃度が６５ｇ／ｌ、フリー硫酸濃度が９０ｇ／ｌの銅電解溶液を用いて、溶液温度４８℃、電流密度１５Ａ／ｄｍ２で電解し、水洗し、粗化処理を行った。Roughening treatment: In Comparative Example 1, the precipitation surface of the electrolytic copper foil was subjected to a roughening treatment by the following two-stage process. The first stage of the roughening treatment uses a copper electrolytic solution for roughening treatment having a copper concentration of 8 g / l, a free sulfuric acid concentration of 50 g / l, a 9-phenylacridine concentration of 150 mg / l, and a chlorine concentration of 50 mg / l. The solution was electrolyzed at a solution temperature of 30 ° C. and a current density of 19 A / dm 2 and washed with water. The second stage uses a copper electrolytic solution having a copper concentration of 65 g / l and a free sulfuric acid concentration of 90 g / l, electrolyzing at a solution temperature of 48 ° C. and a current density of 15 A / dm 2 , washing with water, and roughening treatment. Went.
上述の粗化処理が終了すると、実施例１と同様の防錆処理、シランカップリング剤処理を行って、比較例１の表面処理銅箔を得た。この比較例１の表面処理銅箔の走査型電子顕微鏡観察像を図２に示す。また、評価した諸特性に関しては、実施例との対比が容易となるよう表１に示す。 When the above-mentioned roughening treatment was completed, the same rust prevention treatment and silane coupling agent treatment as in Example 1 were performed, and the surface-treated copper foil of Comparative Example 1 was obtained. A scanning electron microscope observation image of the surface-treated copper foil of Comparative Example 1 is shown in FIG. The evaluated characteristics are shown in Table 1 so as to facilitate comparison with the examples.
［比較例２］
比較例２は、実施例１と同じ電解銅箔を用い、実施例１と同様の析出面に、実施例１と異なる方法で粗化処理を行った。よって、実施例１と粗化処理のみが異なるため、以下において粗化処理に関してのみ詳細に述べる。[Comparative Example 2]
In Comparative Example 2, the same electrolytic copper foil as in Example 1 was used, and the same precipitation surface as in Example 1 was subjected to a roughening treatment by a method different from that in Example 1. Therefore, since only the roughening process is different from the first embodiment, only the roughening process will be described in detail below.
粗化処理： 比較例２は、前記電解銅箔の析出面に対して、以下の方法で粗化処理を行った。粗化処理の１段目は、銅濃度が１８ｇ／ｌ、フリー硫酸濃度が７０ｇ／ｌの粗化処理用銅電解溶液を用いて、溶液温度２５℃、電流密度１０Ａ／ｄｍ２、通電時間１０秒で電解し、水洗した。そして、２段目は、銅濃度が６５ｇ／ｌ、フリー硫酸濃度が６０ｇ／ｌ、の銅電解溶液を用いて、液温４５℃、電流密度１５Ａ／ｄｍ２で、２０秒間電解して粗化処理を行った。Roughening treatment: In Comparative Example 2, a roughening treatment was performed on the deposited surface of the electrolytic copper foil by the following method. The first stage of the roughening treatment uses a copper electrolytic solution for roughening treatment having a copper concentration of 18 g / l and a free sulfuric acid concentration of 70 g / l, a solution temperature of 25 ° C., a current density of 10 A / dm 2 , an energization time of 10 Electrolyzed in seconds and washed with water. In the second stage, using a copper electrolytic solution having a copper concentration of 65 g / l and a free sulfuric acid concentration of 60 g / l, electrolysis is carried out for 20 seconds at a liquid temperature of 45 ° C. and a current density of 15 A / dm 2 for roughening. Processed.
上述の粗化処理が終了すると、実施例と同様の防錆処理、シランカップリング剤処理を行って、比較例２の表面処理銅箔を得た。この比較例２の表面処理銅箔の走査型電子顕微鏡観察像を図３に示す。また、評価した諸特性に関しては、実施例との対比が容易となるよう表１に示す。 When the above-mentioned roughening treatment was completed, the same rust prevention treatment and silane coupling agent treatment as in the example were performed, and the surface-treated copper foil of Comparative Example 2 was obtained. A scanning electron microscope observation image of the surface-treated copper foil of Comparative Example 2 is shown in FIG. The evaluated characteristics are shown in Table 1 so as to facilitate comparison with the examples.
［比較例３］
比較例３は、実施例１と同じ電解銅箔を用い、実施例１で用いた析出面の反対面である電極面に、実施例１と同様の粗化処理、防錆処理、シランカップリング剤処理を行った。よって、実施例１と粗化処理した面が異なるのみであるため、重複した詳細な説明は省略する。この比較例３に係る表面処理銅箔の走査型電子顕微鏡観察像を図４に示す。また、評価した諸特性に関しては、実施例との対比が容易となるよう表１に示す。[Comparative Example 3]
In Comparative Example 3, the same electrolytic copper foil as in Example 1 was used, and the same roughening treatment, rust prevention treatment, and silane coupling as in Example 1 were applied to the electrode surface opposite to the deposition surface used in Example 1. Agent treatment was performed. Therefore, since only the surface subjected to the roughening process is different from that of the first embodiment, a detailed description thereof is omitted. A scanning electron microscope observation image of the surface-treated copper foil according to Comparative Example 3 is shown in FIG. The evaluated characteristics are shown in Table 1 so as to facilitate comparison with the examples.
［評価方法］
うねりの最大高低差（Ｗｍａｘ）： 測定機器としてｚｙｇｏ Ｎｅｗ Ｖｉｅｗ ５０３２（Ｚｙｇｏ社製）を用い、解析ソフトにＭｅｔｒｏ Ｐｒｏ Ｖｅｒ．８．０．２を用いて、低周波フィルタを１１μｍの条件を採用して、うねりの最大高低差（Ｗｍａｘ）を測定した。このとき、表面処理銅箔の被測定面を試料台に密着させて固定し、試料片の１ｃｍ角の範囲内の中で１０８μｍ×１４４μｍの視野を６点選択して測定し、６箇所の測定点から得られたうねりの最大高低差（Ｗｍａｘ）の平均値を代表値として採用した。[Evaluation method]
Maximum height difference of waviness (Wmax): zygo New View 5032 (manufactured by Zygo) was used as a measuring instrument, and Metro Pro Ver. The maximum height difference (Wmax) of the waviness was measured by using the condition of 11 μm for the low frequency filter using 8.0.2. At this time, the surface to be measured of the surface-treated copper foil is fixed in close contact with the sample stage, and 6 fields of 108 μm × 144 μm are selected and measured within the 1 cm square range of the sample piece, and 6 measurements are made. The average value of the maximum height difference (Wmax) of the swell obtained from the points was adopted as a representative value.
明度Ｌ＊： 日本電色工業株式会社製の型式ＳＥ２０００を用いて、ＪＩＳ Ｚ８７２９に準拠して測定した。Lightness L * : Measured according to JIS Z8729 using a model SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.
平均粗さ（Ｒａ）： 小坂研究所製の触針式表面粗さ計 ＳＥ３５００（触針曲率半径：２μｍ）を用い、ＪＩＳ Ｂ０６０１に準拠して測定した。 Average roughness (Ra): Measured in accordance with JIS B0601 using a stylus type surface roughness meter SE3500 (stylus curvature radius: 2 μm) manufactured by Kosaka Laboratory.
銅粒子の付着個数： 実施例に係る黒色化表面処理銅箔の黒色粗化面及び比較例に係る表面処理銅箔の粗化面に対して、斜め４５°方向から観察した電界放射タイプの走査型電子顕微鏡観察像（倍率：２００００倍）における３μｍ×３μｍの領域において観察できる銅粒子の付着個数を目視でカウントした。 Number of adhered copper particles: Field emission type scanning observed from an oblique 45 ° direction with respect to the black roughened surface of the blackened surface-treated copper foil according to the example and the roughened surface of the surface-treated copper foil according to the comparative example. The number of adhered copper particles that can be observed in an area of 3 μm × 3 μm in a scanning electron microscope observation image (magnification: 20000 times) was visually counted.
動摩擦係数： 新東科学株式会社製のトライポギア表面性測定機 ＴＹＰＥ１４を用いて測定した。測定用ステージに厚さ５０μｍのポリイミド樹脂フィルム（宇部興産株式会社製 ユーピレックス）を固定し、このポリイミド樹脂フィルムと表面処理銅箔の粗化面とが対向するように、表面処理銅箔を摩擦子に固定する。そして、垂直荷重１００ｇ、移動速度１００ｍｍ／ｍｉｎ、移動距離１０ｍｍの条件で、測定時間と摩擦抵抗力を出力し、測定値が安定化する２秒〜６秒の間に測定した摩擦力の平均値から動摩擦係数を算出した。 Coefficient of dynamic friction: It was measured using a tripogear surface property measuring machine TYPE 14 manufactured by Shinto Kagaku Co., Ltd. A polyimide resin film with a thickness of 50 μm (Upilex manufactured by Ube Industries Co., Ltd.) is fixed to the measurement stage, and the surface-treated copper foil is frictioned so that the polyimide resin film and the roughened surface of the surface-treated copper foil face each other. To fix. And the average value of the frictional force measured between 2 seconds and 6 seconds when the measurement time and the frictional resistance force are output under the conditions of a vertical load of 100 g, a moving speed of 100 mm / min, and a moving distance of 10 mm. From the above, the dynamic friction coefficient was calculated.
曇り度（Ｈａｚｅ）： 表面処理銅箔とＰＥＴフィルムとを熱圧着して銅張積層板を作製した。その後、当該表面処理銅箔をエッチング除去し、残ったＰＥＴフィルムを、ヘイズメーターＮＤＨ５０００（日本電色工業株式会社製）を用いて、ＪＩＳ−Ｋ７１３６（２０００）に準じて、２３℃でのフィルムの曇り度（Ｈａｚｅ：単位％）を３箇所測定し、その平均値を求めた。 Cloudiness (Haze): A surface-treated copper foil and a PET film were thermocompression bonded to produce a copper-clad laminate. Thereafter, the surface-treated copper foil was removed by etching, and the remaining PET film was subjected to film formation at 23 ° C. according to JIS-K7136 (2000) using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The haze (Haze: unit%) was measured at three locations, and the average value was determined.
［実施例と比較例との対比］
最初に、図面を参照しつつ、実施例と比較例との「うねりの最大高低差（Ｗｍａｘ）」に関して対比する。比較例のうねりの最大高低差（Ｗｍａｘ）の値は、実施例のうねりの最大高低差（Ｗｍａｘ）に比べて高く、これら比較例の曇り度（Ｈａｚｅ）の値も実施例に比べて高く、透明度に欠けることが理解できる。[Contrast between Example and Comparative Example]
First, referring to the drawings, the “maximum difference in waviness (Wmax)” of the example and the comparative example will be compared. The value of the maximum height difference (Wmax) of the waviness of the comparative examples is higher than the maximum height difference (Wmax) of the waviness of the examples, and the haze value (Haze) of these comparative examples is also higher than the examples. It can be understood that transparency is lacking.
しかし、比較例２のうねりの最大高低差（Ｗｍａｘ）は、実施例２のうねりの最大高低差（Ｗｍａｘ）と比べて、大きな差異はないように思われる。しかしながら、曇り度（Ｈａｚｅ）の値をみると、実施例２は１２であるのに対し、比較例２は８４であり、実施例２の場合の樹脂フィルムの透明度が飛躍的に高いことが分かる。そこで、実施例１に係る黒色粗化の状態を示す図１と、比較例２に係る粗化処理の状態を示す図３とを対比すると、全く異なる表面形状をしていることが理解できる。このことから、うねりの最大高低差（Ｗｍａｘ）の値のみが低くとも、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の意図する粗化処理表面が得られていないことが理解できる。 However, it seems that the maximum height difference (Wmax) of the swell in Comparative Example 2 is not significantly different from the maximum height difference (Wmax) of the swell in Example 2. However, looking at the value of haze, Example 2 is 12, whereas Comparative Example 2 is 84. It can be seen that the transparency of the resin film in Example 2 is remarkably high. . Thus, when FIG. 1 showing the black roughening state according to Example 1 is compared with FIG. 3 showing the roughening state according to Comparative Example 2, it can be understood that the surface shape is completely different. From this, even if only the value of the maximum height difference (Wmax) of the swell is low, the intended roughened surface of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application is not obtained. Understandable.
そこで、粗化処理面のＬ＊ａ＊ｂ＊表色系の明度Ｌ＊ 関して、実施例と比較例とを対比してみる。表１の実施例の明度Ｌ＊の値は、実施例１、実施例２、実施例３共に、「明度Ｌ＊ が３０以下」の色調を備えている。これに対し、比較例１及び比較例２の粗化面は、明度Ｌ＊が３０を超えている。そのため、比較例１及び比較例２の曇り度（Ｈａｚｅ）の値が大きくなっていると理解できる。一方、比較例３の粗化面は、実施例３の黒色粗化面よりも暗い色調であり、従来の銅箔の中にも、比較例３のように「明度Ｌ＊ が３０以下」の色調を備えるものがあることが分かる。しかしながら、このとき実施例３の曇り度（Ｈａｚｅ）の値が８であるのに対し、比較例３の曇り度（Ｈａｚｅ）の値は５０と非常に高く、透明度に欠けるものになっている。従って、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ の値のみが良好な黒色を示しても、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔に好ましい黒色粗化面が得られていない場合のあることが理解できる。Therefore, the working example and the comparative example will be compared with respect to L * a * b * color system lightness L * of the roughened surface. The values of the lightness L * of the examples in Table 1 have the color tone of “lightness L * is 30 or less” in both the first, second, and third examples. On the other hand, the lightness L * of the roughened surfaces of Comparative Example 1 and Comparative Example 2 exceeds 30. Therefore, it can be understood that the haze value of Comparative Example 1 and Comparative Example 2 is large. On the other hand, the roughened surface of Comparative Example 3 has a darker color tone than the black roughened surface of Example 3, and in the conventional copper foil, “lightness L * is 30 or less” as in Comparative Example 3. It turns out that there is what has a color tone. However, at this time, the haze value of Example 3 is 8 while the haze value of Comparative Example 3 is as high as 50, which is lacking in transparency. Therefore, even if only the value of the lightness L * of the L * a * b * color system indicates a good black color, the black roughened surface preferable for the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application It can be understood that may not be obtained.
そして、図１と図２〜図４との対比から、銅粒子の付着状態をみるに、比較例に比べ、実施例の銅粒子は微細であり、且つ、均一に多くの銅粒子が付着していることが理解できる。表１から理解できるように、実施例と、比較例１及び比較例２とでは銅粒子の付着個数が明らかに異なっている。このことから、比較例１及び比較例２に比べ、実施例における黒色粗化面は、微細な銅粒子が多く付着することで、良好な黒色の色調を備え、且つ、うねり及び凹凸の無い平坦な表面となっていることが理解できる。一方、比較例３の銅粒子の付着個数は４７１個であり、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の好ましい４００個〜２５００個の銅粒子が付着しているという条件を満たしている。しかし、上述と同様に、比較例３の曇り度（Ｈａｚｅ）の値は５０と非常に高く、透明度に欠けるものになっている。従って、単に付着した銅粒子の個数が適正であっても、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔と同等の黒色粗化面が得られていないことが理解できる。 From the comparison between FIG. 1 and FIG. 2 to FIG. 4, the copper particles in the examples are finer than the comparative example, and a large number of copper particles are uniformly attached. I can understand that. As can be understood from Table 1, the number of adhered copper particles is clearly different between the example and the comparative examples 1 and 2. From this, compared with the comparative example 1 and the comparative example 2, the black roughening surface in an Example has a favorable black color tone by many fine copper particles adhering, and is flat without a wave | undulation and unevenness | corrugation. It can be understood that it is a smooth surface. On the other hand, the number of adhered copper particles of Comparative Example 3 is 471, and the preferred 400 to 2500 copper particles of the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application are adhered. The condition is met. However, similarly to the above, the haze value of Comparative Example 3 is as high as 50 and lacks transparency. Therefore, it can be understood that a black roughened surface equivalent to the blackened surface-treated copper foil for producing a flexible printed wiring board according to the present application is not obtained even if the number of simply attached copper particles is appropriate.
以上のことから理解できるように、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の備える黒色粗化面は、少なくとも、「うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下」という条件と、「Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０以下の色調を備える」という条件とを兼ね備える必要があり、この条件を満たしていればフレキシブルプリント配線板のＣＣＤ視認性及びＡＯＩの検査精度が顕著に向上することが理解できる。そして、更に、この本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔の備える黒色粗化面は、４００個〜２５００個の銅粒子が付着しているという条件を兼ね備えることが、本件出願に言う「曇り度（Ｈａｚｅ）」の値を改善することに有用であると言える。As can be understood from the above, the black roughened surface provided in the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has at least a “maximum undulation height difference (Wmax) of 1.2 μm or less. And the condition that “L * a * b * color system lightness L * has a color tone of 30 or less” must be included. It can be understood that the inspection accuracy of the property and AOI is remarkably improved. And, furthermore, the black roughened surface provided with the blackened surface-treated copper foil for producing the flexible printed wiring board according to the present application has the condition that 400 to 2500 copper particles are attached, It can be said that it is useful for improving the value of “Haze” in the present application.
更に、実施例と比較例との動摩擦係数の値に着目すると、実施例と比較例とに大きな差異はなく、動摩擦係数が０．５０以上であることが理解できる。このことから、本件出願に係る黒色化表面処理銅箔の黒色粗化面が、従来の表面処理銅箔と比べて、微細な凹凸を備えていても、ロールラミネート法で樹脂フィルムと黒色化表面処理銅箔とを積層する際に、黒色化表面処理銅箔と樹脂フィルムとの接着界面で滑りが生じない。また、当該接着界面にシワも気泡も生じることもなく、良好な積層ができるものと判断できる。 Further, focusing attention on the value of the dynamic friction coefficient between the example and the comparative example, it can be understood that there is no significant difference between the example and the comparative example, and the dynamic friction coefficient is 0.50 or more. From this, even if the black roughened surface of the blackened surface-treated copper foil according to the present application has fine irregularities compared to the conventional surface-treated copper foil, the resin film and the blackened surface are obtained by the roll laminating method. When the treated copper foil is laminated, no slip occurs at the adhesive interface between the blackened surface-treated copper foil and the resin film. Moreover, it can be judged that neither good wrinkles nor bubbles are generated at the bonding interface, and that good lamination can be achieved.
上述の実施例及び比較例の製造条件を対比することから明らかなように、本件出願に係る黒色化表面処理銅箔は、うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下の銅箔を用いて、その表面に、９−フェニルアクリジンを含有する黒色粗化用銅電解溶液を用いた黒色粗化を行うことで効率よく生産可能であることが理解できる。 As is clear from the comparison of the manufacturing conditions of the above-described Examples and Comparative Examples, the blackened surface-treated copper foil according to the present application uses a copper foil having a maximum waviness difference (Wmax) of 1.2 μm or less. Thus, it can be understood that the surface can be efficiently produced by performing black roughening using a black roughening copper electrolytic solution containing 9-phenylacridine.
本件出願に係る黒色化表面処理銅箔は、フレキシブルプリント配線板の製造に好適な表面処理銅箔である。この黒色化表面処理銅箔は、ＣＣＤ視認性及びＡＯＩの検出精度を向上させ得る黒色化表面を備えるため、液晶ディスプレイモジュールの接続端子とフレキシブルプリント配線板の接続端子との位置合わせが容易となり、且つ、形成した回路の検査精度が向上し、不良品の流出を効率よく防止できる。また、本件出願に係るフレキシブルプリント配線板製造用の黒色化表面処理銅箔は、微細な黒色粗化粒子が銅で形成されているため、良好なエッチング特性を備え、回路形成時のエッチングにおけるオーバーエッチングの時間を短縮化することが可能となり、ランニングコストの削減が容易となるため好ましい。 The blackened surface-treated copper foil according to the present application is a surface-treated copper foil suitable for manufacturing a flexible printed wiring board. Since this blackened surface-treated copper foil has a blackened surface that can improve CCD visibility and AOI detection accuracy, it is easy to align the connection terminals of the liquid crystal display module and the connection terminals of the flexible printed wiring board, In addition, the inspection accuracy of the formed circuit is improved and the outflow of defective products can be efficiently prevented. In addition, the blackened surface-treated copper foil for manufacturing a flexible printed wiring board according to the present application has good etching characteristics because fine black roughened particles are formed of copper, and over-etching during circuit formation. Etching time can be shortened, and the running cost can be easily reduced, which is preferable.
Claims (9)
当該粗化処理面は、うねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下であり、且つ、Ｌ＊ａ＊ｂ＊表色系の明度Ｌ＊ が３０以下の色調を備える黒色粗化面であることを特徴とするフレキシブルプリント配線板製造用の黒色化表面処理銅箔。 In the surface-treated copper foil provided with the roughened surface for laminating on the resin film ,
The roughened surface is a black roughened surface having a color tone having a maximum waviness difference (Wmax) of 1.2 μm or less and a lightness L * of the L * a * b * color system of 30 or less. A blackened surface-treated copper foil for producing a flexible printed wiring board, characterized in that:
銅箔のうねりの最大高低差（Ｗｍａｘ）が１．２μｍ以下の表面に、銅濃度が１０ｇ／Ｌ〜２０ｇ／Ｌ、フリー硫酸濃度が１５ｇ／Ｌ〜１００ｇ／Ｌ、９−フェニルアクリジン濃度が１００ｍｇ／Ｌ〜２００ｍｇ／Ｌ、塩素濃度が２０ｍｇ／Ｌ〜１００ｍｇ／Ｌの黒色粗化用銅電解溶液を用いて微細銅粒子を付着させて黒色粗化を行うことを特徴とするフレキシブルプリント配線板製造用の黒色化表面処理銅箔の製造方法。 It is a manufacturing method of the blackening surface treatment copper foil for flexible printed wiring board manufacture in any one of Claims 1-5,
On the surface where the maximum height difference (Wmax) of the undulation of the copper foil is 1.2 μm or less, the copper concentration is 10 g / L to 20 g / L, the free sulfuric acid concentration is 15 g / L to 100 g / L, and the 9-phenylacridine concentration is 100 mg. / L-200 mg / L, flexible printed wiring board manufacturing characterized by performing black roughening by attaching fine copper particles using a black roughening copper electrolytic solution having a chlorine concentration of 20 mg / L-100 mg / L For producing a blackened surface-treated copper foil for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014532134A JP5705381B2 (en) | 2013-02-28 | 2014-02-28 | Blackened surface-treated copper foil, method for producing blackened surface-treated copper foil, copper-clad laminate and flexible printed wiring board |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013039388 | 2013-02-28 | ||
| JP2013039388 | 2013-02-28 | ||
| JP2014532134A JP5705381B2 (en) | 2013-02-28 | 2014-02-28 | Blackened surface-treated copper foil, method for producing blackened surface-treated copper foil, copper-clad laminate and flexible printed wiring board |
| PCT/JP2014/055173 WO2014133164A1 (en) | 2013-02-28 | 2014-02-28 | Blackened surface-treated copper foil, method for manufacturing blackened surface-treated copper foil, copper-clad laminate and flexible printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP5705381B2 true JP5705381B2 (en) | 2015-04-22 |
| JPWO2014133164A1 JPWO2014133164A1 (en) | 2017-02-09 |
Family
ID=51428422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014532134A Active JP5705381B2 (en) | 2013-02-28 | 2014-02-28 | Blackened surface-treated copper foil, method for producing blackened surface-treated copper foil, copper-clad laminate and flexible printed wiring board |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5705381B2 (en) |
| KR (2) | KR20150090265A (en) |
| CN (1) | CN105008593B (en) |
| MY (1) | MY181562A (en) |
| TW (1) | TWI690625B (en) |
| WO (1) | WO2014133164A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6539281B2 (en) * | 2014-09-02 | 2019-07-03 | 三井金属鉱業株式会社 | Blackened surface treated copper foil and copper foil with carrier foil |
| JP6734785B2 (en) * | 2014-12-08 | 2020-08-05 | 三井金属鉱業株式会社 | Method for manufacturing printed wiring board |
| CN110072334B (en) * | 2015-01-22 | 2022-04-01 | 三井金属矿业株式会社 | Ultra-thin copper foil with carrier and method for manufacturing the same |
| JP6487704B2 (en) | 2015-02-12 | 2019-03-20 | 福田金属箔粉工業株式会社 | Treated copper foil, copper-clad laminate using the treated copper foil, and printed wiring board |
| JP6293365B2 (en) * | 2015-03-31 | 2018-03-14 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
| JP2017014608A (en) * | 2015-07-06 | 2017-01-19 | 古河電気工業株式会社 | Electrolytic copper foil, lithium ion secondary battery negative electrode and lithium ion secondary battery, printed wiring board, and electromagnetic wave-shielding material |
| US9397343B1 (en) | 2015-10-15 | 2016-07-19 | Chang Chun Petrochemical Co., Ltd. | Copper foil exhibiting anti-swelling properties |
| WO2017179416A1 (en) * | 2016-04-14 | 2017-10-19 | 三井金属鉱業株式会社 | Treated surface copper foil, copper foil with carrier as well as methods for manufacturing copper-clad laminate and printed circuit board using same |
| CN106229344B (en) | 2016-08-19 | 2019-10-15 | 京东方科技集团股份有限公司 | Thin film transistor (TFT), preparation method and display device |
| KR102180926B1 (en) | 2017-06-28 | 2020-11-19 | 에스케이넥실리스 주식회사 | Copper foil having improved workability and charge discharge characteristics, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| TWI694176B (en) * | 2018-08-10 | 2020-05-21 | 南韓商Ｋｃｆ科技有限公司 | Copper foil having improved workability and charge/discharge characteristics, electrode including the same, secondary battery including the same and method for manufacturing the same |
| US11365486B2 (en) | 2018-10-16 | 2022-06-21 | Chang Chun Petrochemical Co., Ltd. | Electrolytic copper foil, electrode comprising the same, and lithium ion battery comprising the same |
| CN111058063B (en) * | 2018-10-16 | 2021-02-02 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising same, and lithium ion battery comprising same |
| JP7352939B2 (en) * | 2019-05-09 | 2023-09-29 | ナミックス株式会社 | composite copper parts |
| JP7456578B2 (en) * | 2019-05-09 | 2024-03-27 | ナミックス株式会社 | Copper surface processing equipment |
| JP7409602B2 (en) * | 2019-05-09 | 2024-01-09 | ナミックス株式会社 | composite copper parts |
| CN116997684A (en) | 2021-03-26 | 2023-11-03 | 三井金属矿业株式会社 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
| JPWO2022202541A1 (en) | 2021-03-26 | 2022-09-29 | ||
| US20240175162A1 (en) | 2021-03-29 | 2024-05-30 | Mitsui Mining & Smelting Co., Ltd. | Roughened copper foil, copper-clad laminate and printed wiring board |
| CN117044412A (en) | 2021-03-29 | 2023-11-10 | 三井金属矿业株式会社 | Roughened copper foil, copper-clad laminate and printed circuit board |
| CN115135043B (en) * | 2022-07-18 | 2023-03-07 | 东莞市国盈电子有限公司 | Sensor circuit board and manufacturing process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004263300A (en) * | 2003-02-12 | 2004-09-24 | Furukawa Techno Research Kk | Copper foil for fine pattern printed circuit and manufacturing method therefor |
| WO2007105635A1 (en) * | 2006-03-10 | 2007-09-20 | Mitsui Mining & Smelting Co., Ltd. | Surface treated elctrolytic copper foil and process for producing the same |
| JP2009004423A (en) * | 2007-06-19 | 2009-01-08 | Hitachi Cable Ltd | Copper foil with carrier foil |
| JP2009176768A (en) * | 2008-01-21 | 2009-08-06 | Ube Ind Ltd | Method for manufacturing copper wiring insulation film using semi-additive method, and copper wiring insulation film manufactured from the same |
| JP2010013738A (en) * | 2004-02-06 | 2010-01-21 | Furukawa Electric Co Ltd:The | Surface treated copper foil and method of producing the same |
| WO2010046804A2 (en) * | 2008-10-21 | 2010-04-29 | Alembic Limited | A process for preparation of losartan potassium form i |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3306404B2 (en) * | 2000-01-28 | 2002-07-24 | 三井金属鉱業株式会社 | Method for producing surface-treated copper foil and copper-clad laminate using surface-treated copper foil obtained by the method |
| JP2004256832A (en) * | 2003-02-24 | 2004-09-16 | Mitsui Mining & Smelting Co Ltd | Surface treated copper foil provided with blackening treated face, and magnetic shielding conductive mesh for front panel of plasma display obtained by using the surface treated copper foil |
| WO2005079130A1 (en) * | 2004-02-17 | 2005-08-25 | Nippon Mining & Metals Co., Ltd. | Copper foil having blackened surface or layer |
| US6979627B2 (en) | 2004-04-30 | 2005-12-27 | Freescale Semiconductor, Inc. | Isolation trench |
| JP2006210689A (en) * | 2005-01-28 | 2006-08-10 | Fukuda Metal Foil & Powder Co Ltd | Copper foil for high frequency printed wiring board and its production method |
| WO2006107043A1 (en) * | 2005-04-04 | 2006-10-12 | Ube Industries, Ltd. | Copper clad laminate |
| JP4958045B2 (en) | 2006-10-27 | 2012-06-20 | 三井金属鉱業株式会社 | Surface-treated copper foil for producing flexible copper-clad laminate and flexible copper-clad laminate obtained using the surface-treated copper foil |
| KR20130098359A (en) * | 2010-10-06 | 2013-09-04 | 후루카와 덴키 고교 가부시키가이샤 | Copper foil and manufacturing method therefor, copper foil with carrier and manufacturing method therefor, printed circuit board, and multilayer printed circuit board |
-
2014
- 2014-02-28 CN CN201480010680.3A patent/CN105008593B/en active Active
- 2014-02-28 JP JP2014532134A patent/JP5705381B2/en active Active
- 2014-02-28 KR KR1020157019621A patent/KR20150090265A/en active Search and Examination
- 2014-02-28 MY MYPI2015702425A patent/MY181562A/en unknown
- 2014-02-28 WO PCT/JP2014/055173 patent/WO2014133164A1/en active Application Filing
- 2014-02-28 KR KR1020167031887A patent/KR102116928B1/en active IP Right Grant
- 2014-03-03 TW TW103106970A patent/TWI690625B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004263300A (en) * | 2003-02-12 | 2004-09-24 | Furukawa Techno Research Kk | Copper foil for fine pattern printed circuit and manufacturing method therefor |
| JP2010013738A (en) * | 2004-02-06 | 2010-01-21 | Furukawa Electric Co Ltd:The | Surface treated copper foil and method of producing the same |
| WO2007105635A1 (en) * | 2006-03-10 | 2007-09-20 | Mitsui Mining & Smelting Co., Ltd. | Surface treated elctrolytic copper foil and process for producing the same |
| JP2009004423A (en) * | 2007-06-19 | 2009-01-08 | Hitachi Cable Ltd | Copper foil with carrier foil |
| JP2009176768A (en) * | 2008-01-21 | 2009-08-06 | Ube Ind Ltd | Method for manufacturing copper wiring insulation film using semi-additive method, and copper wiring insulation film manufactured from the same |
| WO2010046804A2 (en) * | 2008-10-21 | 2010-04-29 | Alembic Limited | A process for preparation of losartan potassium form i |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201447051A (en) | 2014-12-16 |
| JPWO2014133164A1 (en) | 2017-02-09 |
| CN105008593B (en) | 2018-08-24 |
| KR20150090265A (en) | 2015-08-05 |
| MY181562A (en) | 2020-12-29 |
| KR102116928B1 (en) | 2020-05-29 |
| WO2014133164A1 (en) | 2014-09-04 |
| KR20160135369A (en) | 2016-11-25 |
| TWI690625B (en) | 2020-04-11 |
| CN105008593A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5705381B2 (en) | Blackened surface-treated copper foil, method for producing blackened surface-treated copper foil, copper-clad laminate and flexible printed wiring board | |
| JP5180815B2 (en) | Surface-treated electrolytic copper foil and method for producing the same | |
| JP5282675B2 (en) | Copper foil for printed wiring board and method for producing the same | |
| JP5362921B1 (en) | Surface-treated copper foil and laminate using the same | |
| JP2013019056A5 (en) | ||
| JP5706026B1 (en) | Copper foil for wiring board and wiring board | |
| JP5351461B2 (en) | Copper foil and copper foil manufacturing method | |
| JP2014141738A (en) | Surface-treated copper foil and laminate sheet with use of the same | |
| JP2014148691A (en) | Surface-treated copper foil and laminate plate using the same, copper foil, printed wiring board, electronic apparatus, and method for manufacturing printed wiring board | |
| JP5362923B1 (en) | Surface-treated copper foil and laminate using the same | |
| JP5432357B1 (en) | Surface-treated copper foil and laminated board, copper-clad laminated board, printed wiring board and electronic device using the same | |
| JP5362922B1 (en) | Surface-treated copper foil and laminate using the same | |
| JP5362899B1 (en) | Surface-treated copper foil and laminate using the same | |
| JP4999126B2 (en) | Circuit parts | |
| JP2014065974A (en) | Surface-treated copper foil, and laminate, copper-clad laminate, printed-wiring board, and electronic apparatus using the same | |
| JP6845382B1 (en) | Surface-treated copper foil, copper-clad laminate, and printed wiring board | |
| TWI734976B (en) | Surface treatment copper foil, copper clad laminate and printed circuit board | |
| JP2014177712A (en) | Surface-treated copper foil and laminated board using the same, copper foil, printed wiring board, electronic apparatus and method for producing printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150204 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150224 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5705381 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |