JP4341023B2 - Method for producing metal-coated liquid crystal polymer film - Google Patents
Method for producing metal-coated liquid crystal polymer film Download PDFInfo
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- JP4341023B2 JP4341023B2 JP2004118339A JP2004118339A JP4341023B2 JP 4341023 B2 JP4341023 B2 JP 4341023B2 JP 2004118339 A JP2004118339 A JP 2004118339A JP 2004118339 A JP2004118339 A JP 2004118339A JP 4341023 B2 JP4341023 B2 JP 4341023B2
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims description 83
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims description 83
- 229910052751 metal Inorganic materials 0.000 title claims description 81
- 239000002184 metal Substances 0.000 title claims description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 80
- 239000010949 copper Substances 0.000 claims description 78
- 229910052802 copper Inorganic materials 0.000 claims description 78
- 229920001169 thermoplastic Polymers 0.000 claims description 46
- 239000004416 thermosoftening plastic Substances 0.000 claims description 45
- 238000009832 plasma treatment Methods 0.000 claims description 41
- 238000004544 sputter deposition Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 238000007747 plating Methods 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 10
- 230000003746 surface roughness Effects 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 118
- 239000010408 film Substances 0.000 description 117
- 208000028659 discharge Diseases 0.000 description 41
- 229920001721 polyimide Polymers 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
- 239000004642 Polyimide Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Description
本発明は、プリント配線板、フレキシブルプリント配線板、ＴＡＢテープ、ＣＯＦテープ等の電子部品の素材となる金属被覆液晶ポリマーフィルムの製造方法に関するものである。 The present invention relates to a method for producing a metal-coated liquid crystal polymer film as a material for electronic components such as a printed wiring board, a flexible printed wiring board, a TAB tape, and a COF tape.
近年、マイクロエレクトロニクス分野の技術の発展には目覚ましいものがあり、携帯用電子機器等において小型・軽量化の要求が顕著で、高密度実装に対する期待は大きくなっている。
これに伴い、配線板の多層化、配線ピッチの狭幅化、ビアホールの微細化など、より集積化に耐える材料が要求されている。
In recent years, there has been a remarkable development in technology in the field of microelectronics, and there has been a significant demand for miniaturization and weight reduction in portable electronic devices and the like, and expectations for high-density mounting are increasing.
Along with this, there is a demand for materials that can withstand higher integration, such as multilayer wiring boards, narrower wiring pitches, and finer via holes.
かかる要求に応える基板材料としては、例えば、ポリイミドが挙げられる。ポリイミドは、優れた耐熱性を有し、また機械的、電気的および化学的特性において他のプラスチック材料に比べ遜色のないことから、例えば、プリント配線板（ＰＷＢ）、フレキシブルプリント配線板（ＦＰＣ）、テープ自動ボンディング（ＴＡＢ）用テープ、そしてチップオンフィルム（ＣＯＦ）用テープ等の電子部品用の絶縁基板材料として多用されている。
具体的には、上記ＰＷＢ、ＦＰＣ、ＴＡＢテープ、ＣＯＦテープは、ポリイミド基板の少なくとも片面に金属導体層として主に銅を被覆した金属被覆ポリイミド基板を加工することによって製造されている。
An example of a substrate material that meets this requirement is polyimide. Polyimide has excellent heat resistance and is inferior to other plastic materials in mechanical, electrical and chemical properties. For example, printed wiring board (PWB), flexible printed wiring board (FPC) It is widely used as an insulating substrate material for electronic parts such as tapes for automatic tape bonding (TAB) and tapes for chip-on-film (COF).
Specifically, the PWB, FPC, TAB tape, and COF tape are manufactured by processing a metal-coated polyimide substrate mainly coated with copper as a metal conductor layer on at least one surface of a polyimide substrate.
また、金属被覆ポリイミド基板には、ポリイミド基板と銅箔とを接着剤を介して接合した３層銅ポリイミド基板と、ポリイミド基板に直接銅層を形成した２層銅ポリイミド基板があり、更に、２層銅ポリイミド基板には、市販の銅箔にポリイミドを成膜するキャスティング基板と、市販のポリイミドにスパッタリング法および電解めっきまたは無電解めっき、もしくはその両方を併用し、直接金属を積層するめっき法により製造された２層銅ポリイミド基板がある。
このうち、近時の携帯電子機器の小型、薄型化に伴い、上記ＴＡＢテープ、ＣＯＦテープに対しても小型、薄型、すなわち高密度化が要求され、その配線ピッチ（配線幅／スペース幅）は益々微細になっていることから、導体層（銅皮膜）の膜厚を薄く、自由に管理できる２層銅ポリイミド基板が注目されている。
Further, the metal-coated polyimide substrate includes a three-layer copper polyimide substrate obtained by bonding a polyimide substrate and a copper foil via an adhesive, and a two-layer copper polyimide substrate in which a copper layer is directly formed on the polyimide substrate. For the layered copper polyimide substrate, there is a casting substrate that forms a polyimide film on a commercially available copper foil, and a plating method that uses a sputtering method and electrolytic or electroless plating, or both in combination on a commercially available polyimide, and directly laminates the metal. There are manufactured two-layer copper polyimide substrates.
Among these, along with the recent downsizing and thinning of portable electronic devices, the TAB tape and COF tape are also required to be small and thin, that is, high density, and the wiring pitch (wiring width / space width) is Since it has become increasingly finer, a two-layer copper polyimide substrate has attracted attention because the thickness of the conductor layer (copper film) is thin and can be freely controlled.
しかしながら、２層銅ポリイミド基板は初期密着力こそ実用レベルにあるものの、耐熱環境における密着力や高温高湿環境における密着力等、接続信頼性に関わる密着性について従来の３層銅ポリイミド基板と比較して低く、その改善が望まれている。
従って、市場からは３層銅ポリイミド基板と同等の密着力（３００〜４００Ｎ／ｍ程度）を有することが２層銅ポリイミド基板には求められている。
However, although the two-layer copper polyimide substrate has an initial level of adhesion, it has a practical level, but compared to the conventional three-layer copper polyimide substrate in terms of adhesion related to connection reliability such as adhesion in a heat-resistant environment and adhesion in a high-temperature and high-humidity environment. Therefore, the improvement is desired.
Accordingly, the double-layer copper polyimide substrate is required from the market to have an adhesive force (about 300 to 400 N / m) equivalent to that of the three-layer copper polyimide substrate.
ところで、２層めっき基板用フィルムとしては、上記ポリイミドフィルムを始めとする高周波特性や寸法安定性に優れた熱可塑性液晶ポリマーが注目されており、かかる熱可塑性液晶ポリマーはポリマーを構成する分子が容易に配向するので、力学的物性の優れた成形物を与える一方、配向方向に割れ易い、裂け易いという欠点を有する。
このため、例えば、射出成形法により製造された成形物は、その表層部が強い配向のために剥離し、毛羽立ちが生じ易く、そのままでは接着剤との接着不良、印刷インキや導電性塗料との密着不良、無電解めっき層との密着不良となり、しわが発生する等という問題を有する。
また、インフレーション成形法により製造された液晶ポリマーフィルムにおいても同様の問題がある。
By the way, as a film for a two-layer plating substrate, a thermoplastic liquid crystal polymer having excellent high-frequency characteristics and dimensional stability such as the polyimide film has been attracting attention, and the thermoplastic liquid crystal polymer has an easy molecule constituting the polymer. Therefore, it has a drawback that it is easy to crack in the orientation direction and to be easily torn, while giving a molded product having excellent mechanical properties.
For this reason, for example, a molded product produced by an injection molding method peels off due to the strong orientation of the surface layer, and fuzzing is likely to occur, and as such, adhesion failure with the adhesive, printing ink or conductive paint There are problems such as poor adhesion, poor adhesion with the electroless plating layer, and wrinkles.
Moreover, the same problem exists in the liquid crystal polymer film manufactured by the inflation molding method.
かかる液晶ポリマーからなる成形物の表面を改質する方法として、例えば特許文献１にあるように、サンドブラスト処理、クロム酸混液処理、紫外線照射処理等が提案されているが、いずれの方法も実用的な成果は得られていない。
また、特許文献２には、熱可塑性液晶ポリマーフィルムであって、その表面部の酸素原子対炭素原子のモル比が内部の該モル比の１．２倍以上であるフィルムが、接着剤や導電性塗料との親和性が良好で、かつ無電解めっき層との密着性に優れること、かかるフィルムは熱可塑性液晶ポリマーフィルムに、気体状の酸素原子含有化合物の存在下で、気体放電プラズマ処理を施すことにより得られることが記載されており、更に、特許文献３には、液晶ポリマーフィルムに形成する金属コーティング膜の密着性を向上させるために、プラズマエッチングにより液晶ポリマーフィルム表面を粗面化し、パラジウム薄膜を形成した後、めっき法で金属コーティング膜が形成されたフィルムが提案されているが、いずれの場合にも、上記のような機械的特性（密着強度）に優れた金属被覆液晶ポリマーフィルムまでには至っていない。
Patent Document 2 discloses a thermoplastic liquid crystal polymer film having a surface portion in which the molar ratio of oxygen atoms to carbon atoms is 1.2 times or more of the internal molar ratio. The film has a good affinity with the conductive paint and excellent adhesion to the electroless plating layer. Such a film is subjected to a gas discharge plasma treatment on a thermoplastic liquid crystal polymer film in the presence of a gaseous oxygen atom-containing compound. In addition, Patent Document 3 describes that the surface of the liquid crystal polymer film is roughened by plasma etching in order to improve the adhesion of the metal coating film formed on the liquid crystal polymer film. A film in which a metal coating film is formed by a plating method after forming a palladium thin film has been proposed. Properties not reached the stage excellent metallized liquid crystal polymer film (adhesion strength).
本発明の目的は、電子絶縁材料として有用であり、耐熱性、耐薬品性、電気的性質（電気絶縁性、誘電的性質等）等に優れた金属被覆液晶ポリマーフィルムを提供することにあり、より具体的には、放電プラズマ処理された金属被覆液晶ポリマーフィルムと該フィルムの上にスパッタリング法で作製できる金属シード層、該金属シード層と該金属シード層の上にスパッタリング法により形成される銅導電層との親和性、密着性が良好で、さらに該銅導電層の上に湿式めっき法で作製される銅導電層を積層した状態でもスパッタリング法により形成された銅導電層との親和性、密着性に優れた熱可塑性液晶ポリマーフィルムを用いた金属被覆液晶ポリマーフィルムの製造方法を提供することにある。 An object of the present invention is to provide a metal-coated liquid crystal polymer film that is useful as an electronic insulating material and has excellent heat resistance, chemical resistance, electrical properties (electrical insulation, dielectric properties, etc.), and the like. More specifically, a metal-coated liquid crystal polymer film that has been subjected to discharge plasma treatment, a metal seed layer that can be formed on the film by a sputtering method, and a copper that is formed on the metal seed layer and the metal seed layer by a sputtering method Affinity with the conductive layer, good adhesion, and also with the copper conductive layer formed by the sputtering method even when the copper conductive layer produced by the wet plating method is laminated on the copper conductive layer, An object of the present invention is to provide a method for producing a metal-coated liquid crystal polymer film using a thermoplastic liquid crystal polymer film having excellent adhesion.
本発明者は、上記目的を達成するために鋭意検討した結果、熱可塑性液晶ポリマーフィルムの表面に、酸素ガス圧０．６〜２．５Ｐａの雰囲気下で放電プラズマ処理を施した後、該フィルム上にスパッタリング法で金属シード層を形成し、さらにスパッタリング法で銅導電層を形成し、しかも、これら金属シード層と銅導電層の合計の膜厚を０．０５〜１μｍとし、次いで該銅導電層の上に湿式めっき法で１〜３０μｍの膜厚の銅導電層を形成することによって、放電プラズマ処理された金属被覆液晶ポリマーフィルムと該フィルムの上にスパッタリング法で作製できる金属シード層、該金属シード層と該金属シード層の上にスパッタリング法により形成される銅導電層との親和性、密着性が良好で、さらに該銅導電層の上に湿式めっき法で銅導電層を積層した状態でもスパッタリング法により形成された銅導電層との親和性、密着性に優れた金属被覆液晶ポリマーフィルムが得られること、従って、かかる金属被覆液晶ポリマーフィルムは、プリント配線板、フレキシブルプリント配線板、ＴＡＢテープ、ＣＯＦテープ等の電子部品の素材に極めて有用であることを見出し、本発明を完成するに至った。
即ち、本発明に係る金属被覆液晶ポリマーフィルムの製造方法は、熱可塑性液晶ポリマーフィルムと、該フィルム上に形成された金属シード層と、該金属シード層上に形成された銅導電層とからなる金属被覆液晶ポリマーフィルムの製造方法において、熱可塑性液晶ポリマーフィルム表面に酸素ガス圧０．６〜２．５Ｐａの雰囲気下で放電プラズマ処理を施した後、スパッタリング法により合計膜厚が０．０５〜１μｍとなるように金属シード層と銅導電層とを順次形成し、次いで湿式めっき法により合計膜厚が１〜３０μｍとなるように銅導電層を形成したことを特徴とするものである。
また、本発明に係る他の金属被覆液晶ポリマーフィルムの製造方法は、前記熱可塑性液晶ポリマーフィルムの表面粗さは、前記放電プラズマ処理の前後とも、算術平均高さＲａが１０〜１００ｎｍであり、かつ、最大高さＲｚが１００〜１０００ｎｍであることを特徴とし、更に、前記放電プラズマ処理に要する時間は、１０〜１００秒であることを特徴とし、また、前記放電プラズマ処理における対放電電極間に、５００〜３０００Ｖの直流電圧を加えることを特徴とするものである。
As a result of intensive studies to achieve the above object, the present inventor conducted a discharge plasma treatment on the surface of a thermoplastic liquid crystal polymer film in an atmosphere having an oxygen gas pressure of 0.6 to 2.5 Pa, and then the film. A metal seed layer is formed thereon by a sputtering method, a copper conductive layer is further formed by a sputtering method, and the total film thickness of the metal seed layer and the copper conductive layer is set to 0.05 to 1 μm. By forming a copper conductive layer having a thickness of 1 to 30 μm on the layer by a wet plating method, a metal-coated liquid crystal polymer film that has been subjected to a discharge plasma treatment, and a metal seed layer that can be produced on the film by a sputtering method, Good affinity and adhesion between the metal seed layer and the copper conductive layer formed by sputtering on the metal seed layer. Furthermore, copper is deposited on the copper conductive layer by wet plating. A metal-coated liquid crystal polymer film having excellent affinity and adhesion with a copper conductive layer formed by a sputtering method even in a state in which a conductive layer is laminated can be obtained. Therefore, such a metal-coated liquid crystal polymer film is a printed wiring board, The present inventors have found that it is extremely useful as a material for electronic parts such as flexible printed wiring boards, TAB tapes, COF tapes, etc., and completed the present invention.
That is, the method for producing a metal-coated liquid crystal polymer film according to the present invention comprises a thermoplastic liquid crystal polymer film, a metal seed layer formed on the film, and a copper conductive layer formed on the metal seed layer. In the method for producing a metal-coated liquid crystal polymer film, after subjecting the surface of the thermoplastic liquid crystal polymer film to a discharge plasma treatment in an atmosphere having an oxygen gas pressure of 0.6 to 2.5 Pa, the total film thickness is 0.05 to A metal seed layer and a copper conductive layer are sequentially formed so as to have a thickness of 1 μm, and then a copper conductive layer is formed by a wet plating method so that the total film thickness becomes 1 to 30 μm.
Further, in the method for producing another metal-coated liquid crystal polymer film according to the present invention, the surface roughness of the thermoplastic liquid crystal polymer film has an arithmetic average height Ra of 10 to 100 nm before and after the discharge plasma treatment, The maximum height Rz is 100 to 1000 nm, the time required for the discharge plasma treatment is 10 to 100 seconds, and between the counter-discharge electrodes in the discharge plasma treatment. In addition, a DC voltage of 500 to 3000 V is applied.
本発明に係る金属被覆液晶ポリマーフィルムによれば、初期密着力と、１５０℃大気中に１６８時間放置された後の耐熱密着力と、１２１℃、９５％、２気圧、１００時間のＰＣＴ試験後のＰＣＴ密着力とが、いずれも銅導電層の膜厚８μｍにおいて３００Ｎ／ｍ以上となるという優れた機械的強度を得ることが可能となる。
また、本発明に係る金属被覆液晶ポリマーフィルムによれば、放電プラズマ処理された金属被覆液晶ポリマーフィルムと該フィルムの上にスパッタリング法で作製できる金属シード層、該金属シード層と該金属シード層の上にスパッタリング法により形成される銅導電層との親和性、密着性が良好で、さらに該銅導電層の上に湿式めっき法で銅導電層を積層した状態でもスパッタリング法により形成された銅導電層との親和性、密着性に優れた金属被覆液晶ポリマーフィルムが得られる。
このため、本発明に係る金属被覆液晶ポリマーフィルムは、プリント配線板、フレキシブルプリント配線板、ＴＡＢテープ、ＣＯＦテープ等の電子部品の素材に有用となる。
According to the metal-coated liquid crystal polymer film of the present invention, the initial adhesion strength, the heat-resistant adhesion strength after being left in the atmosphere at 150 ° C. for 168 hours, and the PCT test at 121 ° C., 95%, 2 atm, 100 hours. It is possible to obtain an excellent mechanical strength such that the PCT adhesion strength is 300 N / m or more at a copper conductive layer thickness of 8 μm.
According to the metal-coated liquid crystal polymer film of the present invention, the metal-coated liquid crystal polymer film that has been subjected to discharge plasma treatment, a metal seed layer that can be produced on the film by a sputtering method, the metal seed layer, and the metal seed layer Copper conductivity formed by sputtering method even when the copper conductive layer has good affinity and adhesion with the copper conductive layer formed by sputtering method on top of the copper conductive layer. A metal-coated liquid crystal polymer film excellent in affinity with the layer and adhesion can be obtained.
For this reason, the metal-coated liquid crystal polymer film according to the present invention is useful as a material for electronic components such as a printed wiring board, a flexible printed wiring board, a TAB tape, and a COF tape.
以下に本発明について詳細に説明する。
本発明に係る金属被覆ポリマーフィルムの製造方法は、上述のように、熱可塑性液晶ポリマーフィルムと、該フィルム上に形成された金属シード層と、該金属シード層上に形成された銅導電層とからなる金属被覆液晶ポリマーフィルムの製造方法において、熱可塑性液晶ポリマーフィルム表面に酸素ガス圧０．６〜２．５Ｐａの雰囲気下で放電プラズマ処理を施した後、スパッタリング法により合計膜厚が０．０５〜１μｍとなるように金属シード層と銅導電層とを順次形成し、次いで湿式めっき法により合計膜厚が１〜３０μｍとなるように銅導電層を形成したことを特徴とするものである。
The present invention is described in detail below.
As described above, the method for producing a metal-coated polymer film according to the present invention includes a thermoplastic liquid crystal polymer film, a metal seed layer formed on the film, and a copper conductive layer formed on the metal seed layer. In the method for producing a metal-coated liquid crystal polymer film, the surface of the thermoplastic liquid crystal polymer film is subjected to a discharge plasma treatment in an atmosphere having an oxygen gas pressure of 0.6 to 2.5 Pa, and then the total film thickness is set to 0.00 by sputtering. A metal seed layer and a copper conductive layer are sequentially formed to have a thickness of 05 to 1 μm, and then a copper conductive layer is formed to have a total film thickness of 1 to 30 μm by a wet plating method. .
（イ）＜熱可塑性液晶ポリマーフィルム＞
本発明に使用される熱可塑性液晶ポリマーの原料は、特に限定されるものではないが、その具体例として、芳香族または脂肪族ジヒドロキシ化合物、芳香族または脂肪族ジカルボン酸、芳香族ヒドロキシカルボン酸、芳香族ジアミン、芳香族ヒドロキシアミンまたは芳香族アミノカルボン酸に分類される化合物およびその誘導体から導かれる公知のサーモトロピック液晶ポリエステルおよびサーモトロピック液晶ポリエステルアミドを挙げることができる。ただし、光学的に異方性の溶融相を形成し得るポリマーを得るためには、各々の原料化合物の組み合わせには好適な範囲がある。
そして、本発明に使用される金属被覆液晶ポリマーフィルムを構成する熱可塑性液晶ポリマーは、１種類であっても２種類以上の組成物であってもよく、かつ、他の電気絶縁性材料、例えば、酸化アルミニウム等のセラミックス粉体、ポリアリレート、ポリエーテルケトン、ポリアミド、ポリエーテルスルホン、ポリエーテルイミド、ポリイミド、ポリカーボネート、ポリテトラフルオロエチレン、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリ三フッ化塩化エチレン等の熱可塑性ポリマーとの組成物であってもよい。また、前記組成物はアロイ化されたものでもよい。
さらに、本発明に使用される熱可塑性液晶ポリマーには、例えば潤滑剤、酸化防止剤等の添加剤を配合することもできる。
(A) <Thermoplastic liquid crystal polymer film>
The raw material of the thermoplastic liquid crystal polymer used in the present invention is not particularly limited. Specific examples thereof include aromatic or aliphatic dihydroxy compounds, aromatic or aliphatic dicarboxylic acids, aromatic hydroxycarboxylic acids, Mention may be made of known thermotropic liquid crystal polyesters and thermotropic liquid crystal polyester amides derived from compounds classified into aromatic diamines, aromatic hydroxyamines or aromatic aminocarboxylic acids and derivatives thereof. However, in order to obtain a polymer capable of forming an optically anisotropic melt phase, there is a suitable range for the combination of each raw material compound.
The thermoplastic liquid crystal polymer constituting the metal-coated liquid crystal polymer film used in the present invention may be one type or two or more types of compositions, and other electrically insulating materials such as , Ceramic powder such as aluminum oxide, polyarylate, polyetherketone, polyamide, polyethersulfone, polyetherimide, polyimide, polycarbonate, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, polyvinyl fluoride, It may be a composition with a thermoplastic polymer such as polyvinylidene fluoride or poly (ethylene trifluoride) chloride. The composition may be alloyed.
Furthermore, additives such as a lubricant and an antioxidant can be blended with the thermoplastic liquid crystal polymer used in the present invention.
また、本発明に使用される熱可塑性液晶ポリマーとしては、金属被覆液晶ポリマーフィルムの所望の耐熱性および加工性を得る目的においては、約２００〜約４００℃の範囲内、特に約２５０〜約３５０℃の範囲内に融点を有するものが好ましいが、前記フィルム製造の観点からは、比較的低い融点を有するものが好ましい。したがって、より高い耐熱性や融点が必要な場合には、一旦得られたフィルムを加熱処理することによって、所望の耐熱性や融点にまで高めることが有利である。加熱処理の条件の一例を説明すれば、一旦得られたフィルムの融点が２８３℃の場合でも、２６０℃で５時間加熱すれば、融点は３２０℃になる。
更に、本発明に使用される熱可塑性液晶ポリマーフィルムは、熱可塑性液晶ポリマーを押出成形して得られる任意の押出成形法が適用できるが、周知のＴダイ法、ラミネート体延伸法、インフレーション法等が工業的に有利である。特にインフレーション法やラミネート体延伸法では、フィルムの機械軸方向（以下「ＭＤ方向」と略す）だけでなく、これと直交する方向（以下「ＴＤ方向」と略す）にも応力が加えられるため、ＭＤ方向とＴＤ方向における機械的性質および熱的性質のバランスのとれた金属被覆液晶ポリマーフィルムが得られるので、より好適に用いられる。
また、本発明に使用される熱可塑性液晶ポリマーフィルムは、任意の厚みであってよく、１ｍｍ以下の板状またはシート状のものをも包含する。ただし、本発明においては、そのフィルムの膜厚は、２０〜１５０μｍの範囲内にあることが好ましく、２０〜５０μｍの範囲内にあることがより好ましい。金属被覆液晶ポリマーフィルムの膜厚が薄過ぎる場合には、該フィルムの剛性や強度が小さくなるため、得られる配線基板に電子部品を実装する際に加圧により変形して、配線の位置精度が悪化して接続不良の原因となる。
放電プラズマ処理を行う前には、該フィルムの加熱処理を行い、製造工程、保管中に吸着した水分や付着有機成分を脱離させておくことが好ましい。加熱温度は１５０〜２３０℃として５〜１００秒間加熱空間にあれば良い。上記範囲を外れ、加熱温度が低く時間が短い場合は加熱処理の効果が低く、加熱温度が高く加熱時間も長くなると、該熱可塑性液晶ポリマーフィルム自体が変質してしまう場合がある。
The thermoplastic liquid crystal polymer used in the present invention is within the range of about 200 to about 400 ° C., particularly about 250 to about 350 for the purpose of obtaining the desired heat resistance and processability of the metal-coated liquid crystal polymer film. Those having a melting point within the range of ° C. are preferred, but those having a relatively low melting point are preferred from the viewpoint of film production. Therefore, when higher heat resistance and melting point are required, it is advantageous to heat the film once obtained to the desired heat resistance and melting point. If an example of the conditions of heat processing is demonstrated, even if the melting | fusing point of the film obtained once is 283 degreeC, if it heats at 260 degreeC for 5 hours, melting | fusing point will be 320 degreeC.
Furthermore, the thermoplastic liquid crystal polymer film used in the present invention can be applied to any extrusion molding method obtained by extrusion molding of a thermoplastic liquid crystal polymer, but well-known T-die method, laminate stretching method, inflation method, etc. Is industrially advantageous. In particular, in the inflation method and the laminate stretching method, stress is applied not only to the mechanical axis direction of the film (hereinafter abbreviated as “MD direction”) but also to the direction orthogonal to this (hereinafter abbreviated as “TD direction”). Since a metal-coated liquid crystal polymer film having a balanced mechanical property and thermal property in the MD direction and the TD direction can be obtained, it is more preferably used.
Further, the thermoplastic liquid crystal polymer film used in the present invention may have any thickness, and includes a plate-like or sheet-like one having a thickness of 1 mm or less. However, in the present invention, the film thickness of the film is preferably in the range of 20 to 150 μm, and more preferably in the range of 20 to 50 μm. When the film thickness of the metal-coated liquid crystal polymer film is too thin, the rigidity and strength of the film are reduced, so that when the electronic component is mounted on the obtained wiring board, it is deformed by pressure, and the positional accuracy of the wiring is increased. It deteriorates and causes connection failure.
Before performing the discharge plasma treatment, it is preferable to heat-treat the film to desorb moisture adsorbed and adhering organic components during the production process and storage. The heating temperature may be 150 to 230 ° C. and it may be in the heating space for 5 to 100 seconds. When the heating temperature is low and the time is short, the effect of the heat treatment is low. When the heating temperature is high and the heating time is long, the thermoplastic liquid crystal polymer film itself may be deteriorated.
（ロ）＜放電プラズマ処理＞
前記のようにして得られた熱可塑性液晶ポリマーフィルムの表面に、スパッタリング法により金属シード層や銅導電層を密着させるため粗さを発生するための手段としては、放電プラズマ処理が代表的であり、放電プラズマ処理の場合は、直流方式、交流方式どちらでもよい。他に、コロナ放電処理やイオン照射処理等で条件を適宜選択することにより適用でき、その際、表面粗さは、製造条件によって異なるが、本発明に用いるためには、算術平均高さＲａが１０〜１００ｎｍであり、かつ、最大高さＲｚが１００〜１０００ｎｍとなることが好ましい。
即ち、放電プラズマ処理前の粗さと同程度の粗さを放電プラズマ処理後にも保つことが好ましい。従来方法による表面処理では、該熱可塑性液晶ポリマーフィルム表面層だけでなく、さらに内部のフィルムまでを粗くしてしまい、該フィルム上に形成された導電層との密着力は確保できるが、導電層である金属シード層、銅導電層の欠陥の発生につながり好ましくない。また、表面粗さが大きくなることによって、金属シード層による均一な被覆ができなくなり銅導電層から銅が該熱可塑性液晶ポリマーフィルムへ拡散し、それを原因として、該フィルム上に形成された導電層とフィルムの密着力が低下する場合があるからである。
Ｒａ、Ｒｚが前記範囲より外れ大きくなると、該熱可塑性液晶ポリマーフィルム上に形成される金属シード層、銅導電層の欠陥の発生につながり好ましくない。一方、前記範囲より外れ小さくなることは該フィルム上の導電リードのファインピッチ化には有効であるが、該フィルム上に形成された導電層の密着力は低下する傾向になり、また現状安定的に生産することはかなり困難である。
ここで、前記表面粗さは、原子間力顕微鏡ＡＦＭ（Atomic Force Microscopy）を用い、測定範囲：１０μｍ×１０μｍとし測定したものであり、算術平均高さＲａは、粗さ曲線から、その平均線の方向に基準長さだけ抜き取り、この抜き取り部分の方向にＸ軸、縦方向にＹ軸をとり、ｙ＝ｆ（ｘ）で表した時に、下記する数式１によって、
(B) <Discharge plasma treatment>
As a means for generating roughness in order to adhere a metal seed layer or a copper conductive layer to the surface of the thermoplastic liquid crystal polymer film obtained as described above by a sputtering method, a discharge plasma treatment is typical. In the case of discharge plasma treatment, either a DC method or an AC method may be used. In addition, it can be applied by appropriately selecting conditions such as corona discharge treatment or ion irradiation treatment. At that time, the surface roughness varies depending on the production conditions, but for use in the present invention, the arithmetic average height Ra is It is preferably 10 to 100 nm and the maximum height Rz is 100 to 1000 nm.
That is, it is preferable to maintain the same roughness as that before the discharge plasma treatment even after the discharge plasma treatment. In the surface treatment by the conventional method, not only the surface layer of the thermoplastic liquid crystal polymer film, but also the inner film is roughened, and the adhesive force with the conductive layer formed on the film can be secured. This leads to the generation of defects in the metal seed layer and the copper conductive layer. Further, since the surface roughness becomes large, uniform coating with the metal seed layer cannot be performed, and copper diffuses from the copper conductive layer to the thermoplastic liquid crystal polymer film, and the conductive material formed on the film is caused by this. This is because the adhesion between the layer and the film may be reduced.
When Ra and Rz are out of the above ranges and become large, defects in the metal seed layer and the copper conductive layer formed on the thermoplastic liquid crystal polymer film are undesirable. On the other hand, decreasing outside the above range is effective for making fine pitches of the conductive leads on the film, but the adhesion of the conductive layer formed on the film tends to decrease and is stable at present. It is quite difficult to produce.
Here, the surface roughness is measured using an atomic force microscope AFM (Atomic Force Microscopy) with a measurement range of 10 μm × 10 μm, and the arithmetic average height Ra is an average line from the roughness curve. When a reference length is extracted in the direction of X, the X axis is taken in the direction of the extracted portion, the Y axis is taken in the vertical direction, and expressed by y = f (x),
また、最大高さＲｚは、粗さ曲線から、その平均線の方向に基準長さだけ抜き取り、この抜き取り部分の山頂線と谷底線との間隔を粗さ曲線のたて倍率方向に測定した値をいう。前記表面粗さは、ＪＩＳ Ｂ０６０１−２００１に基づいている。
本発明においては、熱可塑性液晶ポリマーフィルム表面に、放電プラズマ処理を施すことが必要である。この放電プラズマ処理は、酸素ガス圧０．６〜２．５Ｐａの雰囲気下で実施する必要があり、この際対放電電極間に５００〜３０００Ｖの直流電圧を加えることが好ましい。また、電力密度としては０．１〜１．５Ｗ／ｃｍ２の範囲となることが望ましい。一方、ガス圧が０．６Ｐａ未満もしくは直流電圧が５００Ｖ未満である場合には、放電が不安定となり表面全体を均一に改質することが難しく、また、表面改質に要する処理時間が長くなる。また、ガス圧が２．５Ｐａを超える場合もしくは直流電圧が３０００Ｖを超える場合には、放電が不安定になるので表面全体の処理の均一性が悪くなるばかりか、金属被覆液晶ポリマーフィルム表面の一部が損傷することもある。
放電プラズマ処理に要する時間は、１０秒以上であればよく、１０〜１００秒の範囲が好ましい。処理時間が１０秒未満の場合には、十分な表面改質効果が得られ難い。一方、１００秒を超える場合には、金属被覆液晶ポリマーフィルムに熱負荷がかかり過ぎ変形してしまうおそれがある。
放電プラズマ処理を施す装置としては、電極の形状には特に制限はなく、平板状、リング状、棒状等各種の形状の電極が使用できる。一対の放電電極はそれぞれ同一の形状でも、また異なった形状でもよい。ロール状の熱可塑性液晶ポリマーフィルムを、放電プラズマ処理装置内部に設置した巻出機から巻出し、一対の放電電極間を通過させて巻取機に導紙させながら、放電プラズマ処理を行う方法が効果的であり好ましい。また、次工程である金属シード層のスパッタリング工程に真空を破らずにフィルムを搬送することが好ましい。
The maximum height Rz is a value obtained by extracting a reference length from the roughness curve in the direction of the average line, and measuring the distance between the peak line and the valley line of the extracted part in the direction of the magnification of the roughness curve. Say. The surface roughness is based on JIS B0601-2001.
In the present invention, it is necessary to subject the thermoplastic liquid crystal polymer film surface to a discharge plasma treatment. This discharge plasma treatment needs to be carried out in an atmosphere having an oxygen gas pressure of 0.6 to 2.5 Pa. At this time, it is preferable to apply a DC voltage of 500 to 3000 V between the counter discharge electrodes. The power density is preferably in the range of 0.1 to 1.5 W / cm 2 . On the other hand, when the gas pressure is less than 0.6 Pa or the DC voltage is less than 500 V, the discharge becomes unstable and it is difficult to uniformly reform the entire surface, and the processing time required for the surface modification becomes longer. . In addition, when the gas pressure exceeds 2.5 Pa or the DC voltage exceeds 3000 V, the discharge becomes unstable, so that the uniformity of the treatment on the entire surface is deteriorated, and the surface of the metal-coated liquid crystal polymer film is reduced. The part may be damaged.
The time required for the discharge plasma treatment may be 10 seconds or more, and is preferably in the range of 10 to 100 seconds. When the treatment time is less than 10 seconds, it is difficult to obtain a sufficient surface modification effect. On the other hand, if it exceeds 100 seconds, the metal-coated liquid crystal polymer film may be excessively deformed and deformed.
As an apparatus for performing the discharge plasma treatment, the shape of the electrode is not particularly limited, and electrodes having various shapes such as a flat plate shape, a ring shape, and a rod shape can be used. The pair of discharge electrodes may have the same shape or different shapes. There is a method in which a roll-shaped thermoplastic liquid crystal polymer film is unwound from an unwinder installed inside the discharge plasma processing apparatus, and is passed through a pair of discharge electrodes and guided to the winder while performing discharge plasma treatment. Effective and preferred. Moreover, it is preferable to convey a film, without breaking a vacuum to the sputtering process of the metal seed layer which is the next process.
（ハ）＜スパッタリング法による金属シード層＞
前記放電プラズマ処理の後、熱可塑性液晶ポリマーフィルム上にニッケル、クロム、またはこれらの合金からなる金属シード層を、スパッタリング法を用いて形成する。
本発明において、熱可塑性液晶ポリマーフィルム表面に、放電プラズマ処理を施した後に、続いてスパッタリング法で金属シード層、続いて後述する銅導電層を形成する順序としているのは、金属シード層は該熱可塑性液晶ポリマーフィルムに対するバリア層の役割を持っており、銅導電層を直接フィルム上に形成すると、銅導電層から銅が該熱可塑性液晶ポリマーフィルムに拡散してフィルム変質層が形成され、該フィルム上に形成された導電層は該変質層とともに、該変質層とフィルムとの境界から剥離しやすくなり、結果として該フィルム上に形成された導電層とフィルムの密着力が低下する場合があるからである。
スパッタリング方法は特に限定されず、直流スパッタリング法、高周波スパッタリング法、マグネトロンスパッタリング法等を用いることができる。例えば、直流マグネトロンスパッタリング法を用いれば、金属シード層として、例えばＮｉＣｒ合金ターゲットを用いて、Ａｒガス圧０．１３Ｐａ〜１．３Ｐａで、スパッタリング電力密度１〜１０Ｗ／ｃｍ２で行うことができる。膜厚は、３〜１００ｎｍ程度の範囲であり、特に、５〜５０ｎｍ程度が密着性の点から好ましい。
(C) <Metal seed layer by sputtering method>
After the discharge plasma treatment, a metal seed layer made of nickel, chromium, or an alloy thereof is formed on the thermoplastic liquid crystal polymer film using a sputtering method.
In the present invention, after the discharge plasma treatment is performed on the surface of the thermoplastic liquid crystal polymer film, the metal seed layer is subsequently formed by a sputtering method, and the copper conductive layer described later is formed in this order. It has a role of a barrier layer for the thermoplastic liquid crystal polymer film, and when a copper conductive layer is formed directly on the film, copper diffuses from the copper conductive layer to the thermoplastic liquid crystal polymer film to form a film altered layer, The conductive layer formed on the film easily peels off from the boundary between the deteriorated layer and the film together with the deteriorated layer, and as a result, the adhesion between the conductive layer formed on the film and the film may be reduced. Because.
The sputtering method is not particularly limited, and a direct current sputtering method, a high frequency sputtering method, a magnetron sputtering method, or the like can be used. For example, if a direct current magnetron sputtering method is used, it can carry out by Ar gas pressure 0.13Pa-1.3Pa and sputtering power density 1-10W / cm < 2 >, for example using a NiCr alloy target as a metal seed layer. The film thickness is in the range of about 3 to 100 nm, and particularly about 5 to 50 nm is preferable from the viewpoint of adhesion.
（ニ）＜スパッタリング法による銅導電層＞
前記金属シード層を形成の後、スパッタリング法で銅導電層を形成し、金属シード層と銅導電層の合計の膜厚を０．０５〜１μｍとする必要がある。好ましくは０．０５〜０．５μｍとし、さらには０．１〜０．３μｍが特性を安定させる上で最も好ましい。膜厚が０．０５μｍ未満の薄さであると後工程の湿式めっき法による銅導電層形成時必要な電流密度で行うことができない。また、銅導電層形成後その表面の酸化層をエッチング処理で除去しようとすると、一部で銅導電層全体が除去されてしまうことがあり好ましくない。一方、膜厚が１μｍよりも厚くなると熱可塑性液晶ポリマーフィルムに熱負荷がかかり変形してしまう。
(D) <Copper conductive layer by sputtering method>
After forming the metal seed layer, a copper conductive layer is formed by sputtering, and the total film thickness of the metal seed layer and the copper conductive layer needs to be 0.05 to 1 μm. Preferably it is 0.05-0.5 micrometer, Furthermore, 0.1-0.3 micrometer is the most preferable when stabilizing a characteristic. When the film thickness is less than 0.05 μm, it cannot be performed at a current density necessary for forming a copper conductive layer by a wet plating method in a subsequent step. Further, if an oxide layer on the surface of the copper conductive layer is formed by etching after the copper conductive layer is formed, the entire copper conductive layer may be partially removed, which is not preferable. On the other hand, when the film thickness is thicker than 1 μm, the thermoplastic liquid crystal polymer film is subjected to a heat load and is deformed.
（ホ）＜湿式めっき法による銅導電層＞
次にスパッタリング法により形成された銅導電層の上に、電気銅めっきもしくは無電解銅めっき、また両者を併用して銅導電層を形成する。本発明で行うポリイミド樹脂表面の無電解めっき前処理および無電解銅めっき処理は特に限定されず公知の方法を用いて良く、例えば触媒付与処理としてはキャタライジング−アクセレレーティング法を用いれば良く、また無電解銅めっき処理としては銅源として硫酸銅、銅錯化剤としてエチレンジアミン四酢酸、還元剤としてホルムアルデヒドを用いためっき液を用いることもできる。
湿式めっき法による銅導電層の膜厚は１〜３０μmの範囲であることが必要であり、好ましくは４〜２０μｍであり、さらには４〜１０μｍの範囲が高精細なパターン形成には最適である。1μｍ未満と薄い場合は、実装工程での接続信頼性が十分に得られない。一方、膜厚が３０μｍを超えて厚くなると膜形成時間が長くなり生産性や経済性に劣るほか、エッチング加工時のパターン形成の困難となり、過度のエッチングによる断線やエッチング残渣によるショート等の不良が発生する傾向にある。
(E) <Copper conductive layer by wet plating method>
Next, a copper conductive layer is formed on the copper conductive layer formed by sputtering using electrolytic copper plating or electroless copper plating, or a combination of both. The electroless plating pretreatment and the electroless copper plating treatment of the polyimide resin surface performed in the present invention are not particularly limited, and a known method may be used, for example, as a catalyst application treatment, a catalyzing-accelrating method may be used. In the electroless copper plating treatment, a plating solution using copper sulfate as a copper source, ethylenediaminetetraacetic acid as a copper complexing agent, and formaldehyde as a reducing agent can be used.
The film thickness of the copper conductive layer by the wet plating method needs to be in the range of 1 to 30 μm, preferably 4 to 20 μm, and further the range of 4 to 10 μm is optimal for high-definition pattern formation. . If the thickness is less than 1 μm, sufficient connection reliability cannot be obtained in the mounting process. On the other hand, if the film thickness exceeds 30 μm, the film formation time becomes longer and the productivity and economy are inferior. Also, pattern formation during etching is difficult, and defects such as disconnection due to excessive etching and shorts due to etching residues are caused. Tend to occur.
前記の製造工程を用いて得られた金属被覆液晶ポリマーフィルムは、作製された状態で測定した初期密着力と、１５０℃大気中に１６８時間放置された後の耐熱密着力と、１２１℃、９５％、２気圧、１００時間のＰＣＴ（Pressure Cooker Test）試験後のＰＣＴ密着力が、いずれも、銅導電層の膜厚８μｍにおいて３００Ｎ／ｍ以上である。
なお、密着力の測定は、いずれも、ＪＰＣＡ ＢＭ０１−１１．５．３に準じて実施した。このとき、密着力は、銅導電層の折り曲げに要する力と界面の接着力の合力であり、銅導電層が厚いほど密着力が大きくなるため、銅導電層の膜厚を８μｍとして測定を行った。
The metal-coated liquid crystal polymer film obtained by using the above-described production process has an initial adhesion measured in the produced state, a heat-resistant adhesion after being left in the atmosphere at 150 ° C. for 168 hours, and 121 ° C. and 95 ° C. %, PCT adhesion after a PCT (Pressure Cooker Test) test at 100 atm for 2 hours is 300 N / m or more at a copper conductive layer thickness of 8 μm.
In addition, all measurement of the adhesive force was implemented according to JPCA BM01-11.5.3. At this time, the adhesion force is the combined force of the force required to bend the copper conductive layer and the adhesive force at the interface. The thicker the copper conductive layer, the greater the adhesion force. Therefore, the copper conductive layer was measured with a film thickness of 8 μm. It was.
以下に本発明の実施例を、比較例と共に具体的に説明するが、本発明は実施例により何ら限定されるものではない。
（実施例１〜６）
Examples of the present invention will be specifically described below together with comparative examples, but the present invention is not limited to the examples.
(Examples 1-6)
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）からなるフィルムの表面を表１に示した条件で放電プラズマ処理を施し、その一部にスパッタリング法でニッケル・クロム合金のシード層および銅導電層を形成した。その後表面の酸化層をエッチング除去し、硫酸銅溶液で電解銅めっきを施し合計膜厚８μｍの金属層を形成させた試料を作製した。
残りの膜形成していない部分について、原子間力顕微鏡ＡＦＭ（DI社製 NS-■ D5000システム）により表面粗さを測定した。
前記金属層を塩化第一鉄溶液によりエッチングし、１ｍｍ幅のパターンを形成し、密着力を測定した。結果を表１に示す。
The surface of a film made of a thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) is subjected to discharge plasma treatment under the conditions shown in Table 1, and a nickel-chromium alloy seed layer and copper conductive material are formed on a part thereof by sputtering. A layer was formed. Thereafter, the oxide layer on the surface was removed by etching and electrolytic copper plating was performed with a copper sulfate solution to prepare a sample in which a metal layer having a total film thickness of 8 μm was formed.
The surface roughness of the remaining portion where no film was formed was measured with an atomic force microscope AFM (NS- ■ D5000 system manufactured by DI).
The metal layer was etched with a ferrous chloride solution to form a 1 mm wide pattern, and the adhesion was measured. The results are shown in Table 1.
（比較例１）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に放電プラズマ処理を施さないこと以外は実施例と同様の手順で金属層を形成した。表面粗さおよび密着力の結果を表１に示す。金属被覆液晶ポリマーフィルムとしては十分な密着力は得られなかった。
(Comparative Example 1)
A metal layer was formed by the same procedure as in the example except that the surface of the thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) was not subjected to discharge plasma treatment. Table 1 shows the results of surface roughness and adhesion. As a metal-coated liquid crystal polymer film, sufficient adhesion was not obtained.
（比較例２）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に酸素ガス圧０．５Ｐａの雰囲気下で放電プラズマ処理を施そうとしたが放電が不安定となり、処理できなかった。
(Comparative Example 2)
An attempt was made to perform a discharge plasma treatment on the film surface of a thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) in an atmosphere with an oxygen gas pressure of 0.5 Pa, but the discharge became unstable and could not be treated.
（比較例３）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に酸素ガス圧３Ｐａの雰囲気下で放電プラズマ処理を施したが、放電後しばらくしてしわが発生した。
(Comparative Example 3)
The surface of the film of thermoplastic liquid crystal polymer (Kexar Co., Ltd. Bexter CT-X100 50 μm) was subjected to a discharge plasma treatment in an atmosphere with an oxygen gas pressure of 3 Pa, but wrinkles were generated after a while.
（比較例４）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に表１に示す条件で５秒間の放電プラズマ処理を施し、実施例１と同様の手順で金属層を形成した。しかし放電プラズマ処理時間が短く、金属被覆液晶ポリマーフィルムとしては十分な密着力は得られなかった。
(Comparative Example 4)
A discharge plasma treatment for 5 seconds was performed on the film surface of a thermoplastic liquid crystal polymer (Kexar Co., Ltd. Bexter CT-X100 50 μm) under the conditions shown in Table 1, and a metal layer was formed in the same procedure as in Example 1. However, the discharge plasma treatment time was short, and sufficient adhesion as a metal-coated liquid crystal polymer film could not be obtained.
（比較例５）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に表１に示す条件で放電プラズマ処理を施し、スパッタリング法により合計膜厚０．０４μｍの金属シード層と銅導電層を形成した。その後、表面の酸化層をエッチング除去し、電解銅めっきを行ったが、銅導電層の厚さが不足して導電性が十分ではなく、特にめっきの初期段階で電流が不安定となり、結果的に膜厚の薄いところができた。
(Comparative Example 5)
A discharge plasma treatment was performed on the film surface of a thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) under the conditions shown in Table 1, and a metal seed layer and a copper conductive layer having a total film thickness of 0.04 μm were formed by a sputtering method. . Thereafter, the oxide layer on the surface was removed by etching and electrolytic copper plating was performed. However, the copper conductive layer was insufficient in thickness, and the conductivity was not sufficient, resulting in unstable current, particularly in the initial stage of plating. The film was thin.
（比較例６）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に表１に示す条件で放電プラズマ処理を施し、スパッタリング法により本発明の範囲内のニッケル・クロム合金層を形成した。続いてスパッタリング法により銅導電層が１．５μｍになるように処理をしていたところ、しばらくしてしわが発生した。
(Comparative Example 6)
A discharge plasma treatment was performed on the film surface of a thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) under the conditions shown in Table 1, and a nickel / chromium alloy layer within the scope of the present invention was formed by a sputtering method. Subsequently, when the copper conductive layer was processed to 1.5 μm by sputtering, wrinkles occurred after a while.
（比較例７）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）のフィルム表面に表１に示す条件で１５０秒間の放電プラズマ処理を施したところ、しばらくしてしわが発生した。
(Comparative Example 7)
When the plasma surface of the thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) was subjected to a discharge plasma treatment for 150 seconds under the conditions shown in Table 1, wrinkles occurred after a while.
（比較例８）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）の表面に表１に示す条件でプラズマ処理を施し、実施例６と同様の手順で金属層を形成した。プラズマ処理電圧が４００Ｖと低く表面処理が不十分であったため、金属層形成樹脂基板としては十分な密着力は得られなかった。
(Comparative Example 8)
Plasma treatment was performed on the surface of a thermoplastic liquid crystal polymer (Kexar Co., Ltd. Bexter CT-X100 50 μm) under the conditions shown in Table 1, and a metal layer was formed in the same procedure as in Example 6. Since the plasma treatment voltage was as low as 400 V and the surface treatment was insufficient, sufficient adhesion as a metal layer-forming resin substrate could not be obtained.
（比較例９）
熱可塑性液晶ポリマー（クラレ社製 ベクスター ＣＴ−Ｘ１００ ５０μｍ）の表面に表１に示す条件でプラズマ処理を施したところ、プラズマ処理電圧が３２００Ｖと高く、処理中しばらくしてしわが発生した。
(Comparative Example 9)
When the surface of a thermoplastic liquid crystal polymer (Kuraray Co., Ltd. Bexter CT-X100 50 μm) was subjected to plasma treatment under the conditions shown in Table 1, the plasma treatment voltage was as high as 3200 V, and wrinkles were generated for a while during the treatment.
表１より分かる通り本発明の実施例によれば、比較例に比べて初期密着力、耐熱密着力、ＰＣＴ密着力共に優れた密着性を示す。 As can be seen from Table 1, according to the examples of the present invention, the initial adhesion, heat-resistant adhesion, and PCT adhesion are superior to those of the comparative examples.
本発明により得られた金属被覆液晶ポリマーフィルムは、初期密着力と、１５０℃大気中に１６８時間放置された後の耐熱密着力と、１２１℃、９５％、２気圧、１００時間のＰＣＴ試験後のＰＣＴ密着力とが、いずれも銅導体層の膜厚８μｍにおいて、３００Ｎ／ｍ以上であり、また、放電プラズマ処理された金属被覆液晶ポリマーフィルムと該フィルムの上にスパッタリング法で作製できる金属シード層、該金属シード層と該金属シード層の上にスパッタリング法により形成される銅導電層との親和性、密着性が良好で、さらに該銅導電層の上に湿式めっき法で作製される銅導電層を積層した状態でもスパッタリング法により作製された銅導電層との親和性、密着性に優れた熱可塑性液晶ポリマーフィルムを用いた金属被覆液晶ポリマーフィルムが得られ、プリント配線板、フレキシブルプリント配線板、ＴＡＢテープ、ＣＯＦテープ等の電子部品用の絶縁基板素材料として有用である。
The metal-coated liquid crystal polymer film obtained by the present invention has an initial adhesion strength, a heat-resistant adhesion strength after being left in the atmosphere at 150 ° C. for 168 hours, and a PCT test at 121 ° C., 95%, 2 atm, 100 hours. PCT adhesion strength is 300 N / m or more when the copper conductor layer has a film thickness of 8 μm, and a metal-coated liquid crystal polymer film subjected to discharge plasma treatment and a metal seed that can be produced on the film by sputtering. Copper having good affinity and adhesion between the metal seed layer and the copper conductive layer formed by sputtering on the metal seed layer, and further prepared by wet plating on the copper conductive layer Metal-coated liquid crystal polymer using thermoplastic liquid crystal polymer film with excellent affinity and adhesion to copper conductive layer produced by sputtering method even when conductive layer is laminated Irumu is obtained, a printed wiring board, a flexible printed wiring board, TAB tape, is useful as an insulating substrate material charges for electronic parts such as COF tape.
Claims (3)
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| JP2004118339A JP4341023B2 (en) | 2004-04-13 | 2004-04-13 | Method for producing metal-coated liquid crystal polymer film |
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| JP2004118339A JP4341023B2 (en) | 2004-04-13 | 2004-04-13 | Method for producing metal-coated liquid crystal polymer film |
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Cited By (1)
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- 2004-04-13 JP JP2004118339A patent/JP4341023B2/en not_active Expired - Lifetime
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| JP2013158935A (en) * | 2012-02-01 | 2013-08-19 | Furukawa Electric Co Ltd:The | Metal-clad laminate, circuit board and method of manufacturing the same |
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