JP2006001185A - Plastic film, metal-coated substrate, and manufacturing method thereof - Google Patents
Plastic film, metal-coated substrate, and manufacturing method thereof Download PDFInfo
- Publication number
- JP2006001185A JP2006001185A JP2004181187A JP2004181187A JP2006001185A JP 2006001185 A JP2006001185 A JP 2006001185A JP 2004181187 A JP2004181187 A JP 2004181187A JP 2004181187 A JP2004181187 A JP 2004181187A JP 2006001185 A JP2006001185 A JP 2006001185A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- film
- plastic film
- substrate
- roughened
- 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.)
- Pending
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 150
- 239000002184 metal Substances 0.000 title claims abstract description 149
- 239000000758 substrate Substances 0.000 title claims abstract description 112
- 239000002985 plastic film Substances 0.000 title claims abstract description 110
- 229920006255 plastic film Polymers 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 238000000034 method Methods 0.000 claims abstract description 65
- 238000007747 plating Methods 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000012808 vapor phase Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 31
- 238000007788 roughening Methods 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 15
- 238000010030 laminating Methods 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 7
- 239000010408 film Substances 0.000 abstract description 92
- 229920001721 polyimide Polymers 0.000 abstract description 34
- 238000004544 sputter deposition Methods 0.000 abstract description 15
- 239000004642 Polyimide Substances 0.000 abstract description 7
- 239000010409 thin film Substances 0.000 abstract description 6
- 238000007740 vapor deposition Methods 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 43
- 239000010949 copper Substances 0.000 description 33
- 229910052802 copper Inorganic materials 0.000 description 29
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 16
- 239000011889 copper foil Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- -1 for example Substances 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 10
- 238000009832 plasma treatment Methods 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 229920005575 poly(amic acid) Polymers 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 108010025899 gelatin film Proteins 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
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- 239000000853 adhesive Substances 0.000 description 4
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- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- SFVSTECQIQQHHL-UHFFFAOYSA-N 1,2-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C1=C(N)C=C2S(=O)(=O)C3=CC(N)=C(C)C(C)=C3C2=C1 SFVSTECQIQQHHL-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- LABVVLMFRIFJRX-UHFFFAOYSA-N 2-[4-[2-[4-(2-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C(=CC=CC=2)N)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC=C1N LABVVLMFRIFJRX-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Moulding By Coating Moulds (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Abstract
【課題】スパッタや蒸着等の気相法によりコストアップを極力抑えながらプラスチックフィルム上に金属薄膜を形成するに当たり、金属とプラスチックフィルムの密着強度の大幅な向上を図る。
【解決手段】基材の表面を粗化面化し（１１０）、その基材の粗化面にポリイミド前駆体を塗布して（１０３）、加熱イミド化する（１０４）ことにより、基材の粗化面に対応した粗化面（Ｒｍｓ０．０５μｍ以上）を有する粗化フィルム１１０を得る。次に基材から剥がした粗化フィルムを真空チャンバ内に収容して、Ｃｒスパッタ（１２２）、Ｃｕスパッタ（１２３）を順にすることにより粗化面上に金属薄膜を形成し、更にその上にＣｕメッキすることにより金属被覆基板１３０を得る。
【選択図】 図１In forming a metal thin film on a plastic film while suppressing cost increase as much as possible by a vapor phase method such as sputtering or vapor deposition, the adhesion strength between the metal and the plastic film is greatly improved.
The surface of a substrate is roughened (110), a polyimide precursor is applied to the roughened surface of the substrate (103), and heated imidized (104) to roughen the substrate. A roughened film 110 having a roughened surface (Rms 0.05 μm or more) corresponding to the roughened surface is obtained. Next, the roughened film peeled off from the substrate is accommodated in a vacuum chamber, and a metal thin film is formed on the roughened surface by sequentially performing Cr sputtering (122) and Cu sputtering (123). A metal-coated substrate 130 is obtained by Cu plating.
[Selection] Figure 1
Description
本発明は、表面に金属膜を被覆することで、フレキシブル回路基板、フレキシブル配線板、あるいはＴＡＢテープ等に用いられる金属被覆プラスチックフィルムなどを作製するのに適したプラスチックフィルム、そのプラスチックフィルムに金属の薄膜を被覆してなる金属被覆基板、及び、それらの製造方法に関する。 The present invention provides a plastic film suitable for producing a metal-coated plastic film used for a flexible circuit board, a flexible wiring board, a TAB tape or the like by coating a metal film on the surface, and a metal film on the plastic film. The present invention relates to a metal-coated substrate coated with a thin film, and a method for producing them.
プラスチックフィルム上に金属を被覆してなる金属被覆基板は、金属被覆部分で回路を形成し、場合によっては、その回路上にＩＣやコンデンサなどのマイクロチップを積載することで、携帯電話やデジタルカメラなどの電子機器を高密度実装化するための必須材料となっている。 A metal-coated substrate made by coating a metal on a plastic film forms a circuit with the metal-coated portion, and in some cases, a microchip such as an IC or a capacitor is mounted on the circuit, so that a mobile phone or digital camera It is an indispensable material for high-density mounting of electronic devices such as.
この種の金属被覆基板の金属としては、価格、加工性、電気的特性、耐マイグレーション性などの面から、銅が最も多く用いられている。また、基板材料であるプラスチックフィルムとしては、用途によって、ポリイミドフィルムやポリエステルフィルムなどが用いられている。 As the metal of this type of metal-coated substrate, copper is most frequently used from the viewpoints of price, workability, electrical characteristics, migration resistance, and the like. Moreover, as a plastic film which is a substrate material, a polyimide film, a polyester film, or the like is used depending on applications.
この金属被覆基板の製造方法としては、
（１）圧延法ないし電解法を用いて予め銅箔を作製し、接着剤でプラスチックフィルムに接合する方法、
（２）接着剤を介さず、プラスチックフィルムの前駆体を銅箔に塗布し、前記前駆体を重合させて接着させるキャスティング法（例えば、特許文献１参照）、
（３）熱可塑性プラスチックフィルムを銅箔と積層してラミネートするラミネート法（例えば、特許文献２参照）、
（４）プラスチックフィルムにスパッタなどで金属を薄く被覆し、その上にメッキで金属を所定の厚さまで被覆する蒸着メッキ法（例えば、特許文献３参照）
などが用いられている。
As a manufacturing method of this metal-coated substrate,
(1) A method of producing a copper foil in advance using a rolling method or an electrolytic method, and bonding it to a plastic film with an adhesive,
(2) A casting method in which a plastic film precursor is applied to a copper foil without using an adhesive, and the precursor is polymerized and bonded (for example, see Patent Document 1).
(3) Laminating method in which a thermoplastic film is laminated with a copper foil (for example, see Patent Document 2),
(4) Evaporation plating method in which a metal is thinly coated on a plastic film by sputtering or the like, and the metal is coated on the plastic film to a predetermined thickness by plating (for example, see Patent Document 3)
Etc. are used.
しかしながら、上記の手法において、（１）の接着剤を用いた手法では、銅箔とプラスチックフィルムとの高温密着安定性が低いために、所定のチップ部品を高温接着処理が必要な半田材を用いて積層することができないという問題があった。 However, in the above method, since the high temperature adhesion stability between the copper foil and the plastic film is low in the method using the adhesive of (1), a solder material that requires high temperature bonding treatment for a predetermined chip component is used. There was a problem that they could not be laminated.
また、（２）、（３）の接着剤を使用しないキャスティング法やラミネート法は、比較的高温密着性に優れているため、チップ部品を実装するような用途に広く用いられているが、例えば、携帯電話の屈曲部等の用途向けには更なる密着性の向上が望まれていた。また近年では、高密度実装化の要望が一層高まり、回路の高精細化対応のために、被覆金属をより薄くしたいとの要望が高まっている。 In addition, the casting method and the laminating method that do not use the adhesive of (2) and (3) are relatively excellent in high-temperature adhesion, and thus are widely used for mounting chip components. Further, it has been desired to further improve the adhesion for applications such as bent portions of mobile phones. In recent years, there has been an increasing demand for high-density mounting, and there has been an increasing demand for a thinner coating metal in order to cope with higher definition of circuits.
この要望を満足するために、キャスティング法やラミネート法においては、なるべく薄い銅箔を用いてプラスチックフィルムをキャスト成膜したり、積層ラミネートしたりしているが、この銅箔として、薄いものを作製し接着することには限界がある。というのは、例えば、膜厚９μｍ以下の銅箔を電解法や圧延法で作製したとしても、貼り付け加工などの際にハンドリング性が悪く、皺などの発生が起こったりする問題がある。 In order to satisfy this demand, in casting and laminating methods, plastic films are cast and laminated using as thin a copper foil as possible, but as this copper foil, a thin one is produced. However, there are limits to bonding. This is because, for example, even if a copper foil having a film thickness of 9 μm or less is produced by an electrolytic method or a rolling method, there is a problem that handling properties are poor at the time of affixing processing and wrinkles are generated.
そこで、予め厚物の銅箔を貼り付けておき、後の工程で、薬品によるエッチング等により銅箔を薄く加工したり、予めバッファ層を積層しておき、積層後にバッファ層を引き剥がすなどして薄膜化を達成したりしている（例えば、特許文献４参照）。しかし、エッチング法では均一にエッチングする技術が難しいために生産性が低く、また、バッファ層を用いる方法では、２種以上の金属箔を積層することになるため、いずれもコストが高いものとなっている。さらに、得られる金属被膜とプラスチックフィルムとの密着性に関しても、十分な性能は得られていない。 Therefore, a thick copper foil is pasted in advance, and the copper foil is processed thinly by chemical etching, etc. in a later process, or a buffer layer is laminated in advance, and the buffer layer is peeled off after lamination. Thus, thinning is achieved (see, for example, Patent Document 4). However, the etching method is difficult because the technique for uniformly etching is difficult, and the productivity is low. In the method using the buffer layer, two or more kinds of metal foils are laminated, so both of them are expensive. ing. Furthermore, sufficient performance is not obtained also about the adhesiveness of the metal coating obtained and a plastic film.
一方、（４）の蒸着メッキ法においては、比較的低コストで、薄い金属膜をプラスチックフィルム上に被覆することが可能となるが、プラスチックフィルムと被覆金属との接着安定性が圧倒的に劣っているという問題点があった。 On the other hand, in the vapor deposition plating method of (4), it is possible to coat a thin metal film on a plastic film at a relatively low cost, but the adhesion stability between the plastic film and the coated metal is overwhelmingly inferior. There was a problem that.
この問題点を解決する手段としては、
（５）蒸着メッキ前に、プラズマ処理によりプラスチックフィルム（例えば、ポリイミドフィルム）の表面を改質する手法、
が行われている。（例えば、非特許文献１参照）。
As a means to solve this problem,
(5) A method of modifying the surface of a plastic film (for example, a polyimide film) by plasma treatment before vapor deposition plating,
Has been done. (For example, refer nonpatent literature 1).
（５）に示した、蒸着メッキ前に、プラズマ処理によりプラスチックフィルムの表面を改質する手法により、蒸着メッキ前にプラスチックフィルム（例えば、ポリイミドフィルム）上へプラズマ処理を行うと、プラスチックフィルム中の化学結合が切断され（ポリイミドフィルムの場合は、ケトン基のＣ−ＣやＣ−Ｎ結合が切断される。）て極性基が形成され、これが被覆金属とイオン結合すると考えられる。 When plasma treatment is performed on a plastic film (for example, polyimide film) before vapor deposition plating by the method of modifying the surface of the plastic film by plasma treatment before vapor deposition plating as shown in (5), The chemical bond is cut (in the case of a polyimide film, the C—C or C—N bond of the ketone group is cut) to form a polar group, which is considered to be ionically bonded to the coating metal.
ここで、このプラズマ処理においては、プラスチックフィルムの表面粗さも大きくなり、二乗平均粗さ（Ｒｍｓ）で２００ｎｍ（０．２μｍ）付近まで粗化面化可能であることが示唆されている。そして、このプラスチックフィルムの粗化面化がアンカー効果を発揮し、上述した金属膜とプラスチックフィルムとの密着性向上の要因となるとも考えられる。しかしながら、当該プラスチックフィルムの二乗平均粗さＲｍｓが約１０ｎｍ以上となると、上述した金属膜とプラスチックフィルムとの密着性向上は飽和してしまっていることから（非特許文献１の図４参照。）、当該プラスチックフィルム表面の二乗平均粗さＲｍｓと金属膜の密着強度との間には、相関が無いことが考察される。つまり、プラズマ処理によりプラスチックフィルム上を粗化面化する手法では密着強度の向上に格別の効果を得ることができないことが知られていた。 Here, in this plasma treatment, it is suggested that the surface roughness of the plastic film also increases, and it is possible to roughen the surface to a mean square roughness (Rms) of around 200 nm (0.2 μm). And it is thought that this roughening of the plastic film exhibits an anchor effect and becomes a factor for improving the adhesion between the metal film and the plastic film described above. However, when the square average roughness Rms of the plastic film is about 10 nm or more, the above-described improvement in adhesion between the metal film and the plastic film is saturated (see FIG. 4 of Non-Patent Document 1). It is considered that there is no correlation between the mean square roughness Rms of the plastic film surface and the adhesion strength of the metal film. That is, it has been known that the method of roughening the surface of the plastic film by plasma treatment cannot obtain a special effect in improving the adhesion strength.
本発明は、上記事情を考慮してなされたもので、プラスチックフィルム上に、気相法により金属膜を形成するに当たり、コストアップを極力抑えながら金属とプラスチックフィルムとの密着強度を大幅に向上できる、基板部材としてのプラスチックフィルム、該プラスチックフィルムを使用した金属被覆基板、及びそれらの製造方法を提供することを目的とする。 The present invention has been made in consideration of the above circumstances, and in forming a metal film on a plastic film by a vapor phase method, the adhesion strength between the metal and the plastic film can be greatly improved while suppressing an increase in cost as much as possible. Another object of the present invention is to provide a plastic film as a substrate member, a metal-coated substrate using the plastic film, and a method for producing them.
上記の課題を解決するために、本発明者等は、まずプラズマによる粗化面化処理が行われたプラスチックフィルム表面について研究を行った。具体的な研究内容として、例えば、（株）キーエンス製の超深度形状測定顕微鏡VK-8500を用い、プラスチックフィルムとしてデュポン製のポリイミドフィルム（製品名カプトン）にプラズマを40分間照射して処理した表面の代表的な部分149×112μｍの範囲を測定レンジ０．０２μm、白黒超深度で観察した。この観察の結果、得られた顕微鏡写真を図２に示す。また、この観察の結果、図２の顕微鏡写真上にＡ−Ｂで示した線に沿って111.7μｍの距離に渡り表面の凹凸を計測した。その結果を図３に示す。 In order to solve the above problems, the present inventors first studied the surface of a plastic film that has been subjected to a roughening surface treatment using plasma. Specifically, for example, a surface treated by irradiating plasma on DuPont polyimide film (product name: Kapton) as a plastic film using VK-8500, a key depth microscope made by Keyence Corporation. A typical area of 149 × 112 μm was observed at a measurement range of 0.02 μm and black and white ultra-deep. As a result of this observation, the micrograph obtained is shown in FIG. Further, as a result of this observation, the surface irregularities were measured over a distance of 111.7 μm along the line indicated by AB on the micrograph of FIG. The result is shown in FIG.
また、図２に示した測定範囲から20×20μｍの領域を任意に５点選び、その各領域内における平均粗さＲａ、最大凹凸高さＲｙ、１０点平均粗さＲｚ、二乗平均粗さRsmを計測した。その計測結果の平均値を図４に示す。 Further, five points of 20 × 20 μm are arbitrarily selected from the measurement range shown in FIG. 2, and the average roughness Ra, the maximum unevenness height Ry, the 10-point average roughness Rz, and the mean square roughness Rsm in each region. Was measured. The average value of the measurement results is shown in FIG.
次に、プラズマ処理時間を上述した４０分間から、２０分間、５分間、プラズマ照射なし、と変化させた後、同様に、測定範囲内の任意５領域におけるＲａ、最大凹凸高さＲｙ、１０点平均粗さＲｚ、二乗平均粗さRsmを各々計測した。その計測結果の平均値を図８に示す。 Next, after changing the plasma processing time from 40 minutes as described above to 20 minutes, 5 minutes, no plasma irradiation, similarly, Ra in any five regions within the measurement range, maximum unevenness height Ry, 10 points Average roughness Rz and root mean square roughness Rsm were measured. The average value of the measurement results is shown in FIG.
これらの計測結果から、本発明者らは以下のような知見を得た。
すなわち、プラスチックフィルム表面を粗面化するためにプラズマ照射による処理を行った場合、平均粗さＲａを大きくするためにはプラズマ照射時間を延長する。すると、プラスチックフィルム表面には、深い凹と高い凸とを有する凹凸が寡占的に生成することが判明した。そして、この深い凹と高い凸とを有する凹凸は、アンカーとしての効果を発揮し得ないものと考えられる。そして、プラスチックフィルム表面における、深い凹と高い凸とを有する凹凸の存在割合は、平均粗さＲａと最大凹凸高さＲｙとの比（Ｒｙ／Ｒａ）で表現することができる。このＲｙ／Ｒａが、例えば８０以上となった場合は、深い凹と高い凸とを有する凹凸の寡占的状態が過剰となり、当該凹凸がアンカーとしての役割を果たすことができず、金属膜とプラスチックフィルムとの密着性が飽和してしまう原因であることに想到した。
From these measurement results, the present inventors obtained the following knowledge.
That is, when processing by plasma irradiation is performed to roughen the plastic film surface, the plasma irradiation time is extended in order to increase the average roughness Ra. Then, it turned out that the unevenness | corrugation which has a deep dent and a high convexity is produced exclusively on the plastic film surface. And it is thought that the unevenness | corrugation which has this deep concave and high convex cannot exhibit the effect as an anchor. And the presence ratio of the unevenness | corrugation which has a deep recessed part and a high unevenness | corrugation in the plastic film surface can be represented by ratio (Ry / Ra) of average roughness Ra and maximum uneven | corrugated height Ry. When this Ry / Ra is, for example, 80 or more, the oligopolistic state of irregularities having deep depressions and high irregularities becomes excessive, and the irregularities cannot serve as anchors, and metal films and plastics It was thought that this was a cause of saturation of adhesion with the film.
上述の推察に基づき、本発明者らは、金属とプラスチックフィルムとの密着強度を大幅に向上できるプラスチックフィルム表面の粗化面の構造とは、表面平均粗さＲａが好ましくは０．０９μm以上のとき、Ｒｙ／Ｒａが４０以下のものであることを見出した。
なお、プラスチックフィルム表面の表面平均粗さＲａは、０．０９μm以上であれば所定の密着性が得られるが、１μmを超えると、プラスチックフィルム表面上に被覆された金属膜をエッチングして回路パターンを形成する際に、当該エッチング精度が低下してしまう。
Based on the above-mentioned inference, the inventors of the present invention have a rough surface structure on the surface of the plastic film that can significantly improve the adhesion strength between the metal and the plastic film. The surface average roughness Ra is preferably 0.09 μm or more. It was found that Ry / Ra was 40 or less.
If the surface roughness Ra of the plastic film surface is 0.09 μm or more, a predetermined adhesion can be obtained. If the surface roughness Ra exceeds 1 μm, the metal film coated on the plastic film surface is etched to form a circuit pattern. The etching accuracy is lowered when forming the film.
次に、本発明者らは、上述の、表面の表面平均粗さＲａが好ましくは０．０９μm以上で、Ｒｙ／Ｒａが好ましくは４０以下の構造を持った粗化面を有するプラスチックフィルムの製造方法を研究した。 Next, the inventors of the present invention produce a plastic film having a roughened surface having a structure in which the surface average roughness Ra is preferably 0.09 μm or more and Ry / Ra is preferably 40 or less. The method was studied.
多数の試行錯誤において、本発明者らは、プラズマ処理によらないプラスチックフィルムの粗化面化処理方法をも検討したが、平滑なプラスチックフィルムを形成した後、サンドブラスト等を用いて、表面を粗化面化する手法では、やはり極端な凹凸部や亀裂が発生し、所定の粗さを有する粗化面を得ることが難しかった。そして、さらに検討を重ねた結果、プラスチックフィルムの形成時に、所定の粗化面を有する基材上で当該プラスチックフィルムを形成することにより、上述の構造を持った粗化面を有するプラスチックフィルムを製造できることを見出した。 In many trials and errors, the present inventors also examined a roughening treatment method for a plastic film that does not depend on plasma treatment, but after forming a smooth plastic film, the surface was roughened using sandblasting or the like. In the method of making the surface rough, extreme uneven portions and cracks are also generated, and it is difficult to obtain a roughened surface having a predetermined roughness. As a result of further studies, a plastic film having a roughened surface having the above-described structure is produced by forming the plastic film on a substrate having a predetermined roughened surface when forming the plastic film. I found out that I can do it.
そして、この所定の粗化面を有する基材上で形成したプラスチックフィルムの粗化面に金属膜を被覆したところ、プラズマ処理による粗化面化処理とは異なって、プラスチックフィルムと金属膜との密着強度が著しく向上していることを見出し、本発明を成すことができた。つまり、本願発明は、以下の構成を有する。 Then, when the metal film is coated on the roughened surface of the plastic film formed on the substrate having the predetermined roughened surface, unlike the roughened surface treatment by the plasma treatment, the plastic film and the metal film are It was found that the adhesion strength was remarkably improved, and the present invention could be achieved. That is, the present invention has the following configuration.
第１の構成は、少なくとも片面の表面平均粗さＲａが０．０９μm以上であり、表面平均粗さＲａと最大凹凸高さＲｙとの比Ｒｙ／Ｒａが４０以下であることを特徴とするプラスチックフィルムである。 The first structure is a plastic characterized in that the surface average roughness Ra of at least one surface is 0.09 μm or more, and the ratio Ry / Ra between the surface average roughness Ra and the maximum unevenness height Ry is 40 or less. It is a film.
第２の構成は、第１の構成に記載のプラスチックフィルムに、金属膜が被覆されたものであることを特徴とする金属被覆基板である。 The second configuration is a metal-coated substrate characterized in that the plastic film described in the first configuration is coated with a metal film.
第３の構成は、第２の構成に記載の金属被覆基板の金属膜上に、更にメッキ法による金属膜が積層されていることを特徴とする金属被覆基板である。 The third configuration is a metal-coated substrate in which a metal film by a plating method is further laminated on the metal film of the metal-coated substrate described in the second configuration.
第４の構成は、基材の表面を粗化面化する基材表面粗化面化処理工程と、
該基材表面粗化面処理工程により得られた基材の粗化面にプラスチックフィルムまたはその前駆体を接触させることにより、前記基材の粗化面に対応した粗化面を有するプラスチックフィルムを形成する粗化フィルム形成工程と、を備えることを特徴とするプラスチックフィルムの製造方法である。
A 4th structure is a base-material surface roughening surface treatment process which roughens the surface of a base material,
A plastic film having a roughened surface corresponding to the roughened surface of the substrate is obtained by bringing a plastic film or a precursor thereof into contact with the roughened surface of the substrate obtained by the roughened surface treatment step of the substrate surface. And a roughening film forming step for forming the plastic film.
第５の構成は、第４の構成に記載のプラスチックフィルムの製造方法において、前記基材表面粗化面化処理工程とは、前記基材の表面を表面平均粗さＲａが０．０５μm以上であり、表面平均粗さＲａと最大凹凸高さＲｙとの比Ｒｙ／Ｒａが４０以下であるように粗化面化する基材表面粗化面化処理工程であることを特徴とするプラスチックフィルムの製造方法である。 According to a fifth configuration, in the plastic film manufacturing method according to the fourth configuration, the surface roughening treatment step of the substrate has a surface average roughness Ra of 0.05 μm or more on the surface of the substrate. A plastic film characterized by being a base surface roughening surface treatment step for roughening the surface so that the ratio Ry / Ra of the surface average roughness Ra to the maximum unevenness height Ry is 40 or less It is a manufacturing method.
第６の構成は、第４または５の構成に記載のプラスチックフィルムの製造方法により製造されたプラスチックフィルムの前記粗化面上へ、気相法により金属膜を形成する、金属膜形成工程を備えることを特徴とする金属被覆基板の製造方法である。 The sixth configuration includes a metal film forming step of forming a metal film by a vapor phase method on the roughened surface of the plastic film manufactured by the plastic film manufacturing method according to the fourth or fifth configuration. This is a method for producing a metal-coated substrate.
第７の構成は、第６の構成に記載の金属被覆基板の製造方法により製造された金属被覆基板の前記金属膜上へ、メッキ法により同種または異種の金属膜を積層形成するメッキ成膜工程を備えることを特徴とする金属被覆基板の製造方法である。 In the seventh configuration, a plating film forming step of laminating and forming the same or different metal films by plating on the metal film of the metal-coated substrate manufactured by the method of manufacturing a metal-coated substrate described in the sixth configuration It is a manufacturing method of the metal-coated board | substrate characterized by including.
第８の構成は、第６または第７の構成に記載の金属被覆基板の製造方法により製造された金属被覆基板の前記金属膜にエッチング加工を施すことにより、所定の回路を形成することを特徴とする金属被覆基板の製造方法である。 The eighth configuration is characterized in that a predetermined circuit is formed by etching the metal film of the metal-coated substrate manufactured by the method for manufacturing a metal-coated substrate according to the sixth or seventh configuration. This is a method for producing a metal-coated substrate.
第１の構成を有するプラスチックフィルムは、金属膜が被覆される表面の表面平均粗さRaを０．０９μm以上とし、表面平均粗さRaと最大凹凸高さRyとの比Ry/Raを40以下としたことで、金属膜とプラスチックフィルムとの密着性を大幅に向上させることができるプラスチックフィルムである。 The plastic film having the first structure has a surface average roughness Ra of 0.09 μm or more on the surface on which the metal film is coated, and a ratio Ry / Ra between the surface average roughness Ra and the maximum unevenness height Ry is 40 or less. Thus, the plastic film can greatly improve the adhesion between the metal film and the plastic film.
第２の構成を有する金属被覆基板は、当該金属被覆基板を構成する金属膜とプラスチックフィルムとの密着性が大幅に向上しているため、金属膜とプラスチックフィルムとの密着強度が高い金属被覆基板である。 In the metal-coated substrate having the second configuration, since the adhesion between the metal film and the plastic film constituting the metal-coated substrate is greatly improved, the metal-coated substrate having a high adhesion strength between the metal film and the plastic film. It is.
第３の構成を有する金属被覆基板は、金属膜の上に更にメッキ法による金属膜を積層しているので、金属膜の厚さが自由に効率良く制御された金属被覆基板である。 The metal-coated substrate having the third configuration is a metal-coated substrate in which the thickness of the metal film is freely and efficiently controlled because a metal film obtained by plating is further laminated on the metal film.
第４の構成を有するプラスチックフィルムの製造方法によれば、予め基材を粗化面化し、その基材の粗化面にプラスチックフィルムまたはその前駆体を接触させることで、粗化面を有するプラスチックフィルムを形成することができる。 According to the method for producing a plastic film having the fourth structure, the plastic having the roughened surface is obtained by previously roughening the base material and bringing the plastic film or its precursor into contact with the roughened surface of the base material. A film can be formed.
第５の構成を有するプラスチックフィルムの製造方法によれば、予め基材の表面を表面平均粗さＲａが０．０５μm以上であり、表面平均粗さＲａと最大凹凸高さＲｙとの比Ｒｙ／Ｒａが４０以下であるように粗化面化したことで、その基材の粗化面にプラスチックフィルムまたはその前駆体を接触させることで、所定の粗化面を有するプラスチックフィルムを再現性良く形成することができる。
第６の構成を有する金属被覆基板の製造方法によれば、第４または５の構成により製造されたプラスチックフィルムの粗化面上へ、気相法により金属膜を形成するので、金属被覆とプラスチックフィルムとの密着性が大幅に高められた金属被覆基板を容易に得ることができる。
According to the method for producing a plastic film having the fifth configuration, the surface average roughness Ra of the surface of the substrate is 0.05 μm or more in advance, and the ratio Ry / the surface average roughness Ra to the maximum unevenness height Ry By roughening the surface so that Ra is 40 or less, a plastic film having a predetermined roughened surface is formed with good reproducibility by bringing the plastic film or its precursor into contact with the roughened surface of the base material. can do.
According to the method of manufacturing the metal-coated substrate having the sixth configuration, the metal film is formed on the roughened surface of the plastic film manufactured by the fourth or fifth configuration by the vapor phase method. It is possible to easily obtain a metal-coated substrate whose adhesion to the film is greatly enhanced.
第７の構成を有する金属被覆基板の製造方法によれば、第６の構成により製造された金属被覆基板の金属膜の上に同種または異種の金属の薄膜をメッキ法により積層形成するので金属膜の厚さを自由に効率良く制御することができる。 According to the method of manufacturing the metal-coated substrate having the seventh configuration, the metal film is formed by laminating the same or different metal thin films on the metal film of the metal-coated substrate manufactured by the sixth configuration by the plating method. Can be controlled freely and efficiently.
第８の構成を有する金属被覆基板の製造方法によれば、第６または第７の構成により製造された金属被覆基板にエッチング加工を施すことにより、金属膜部分により所定の回路を形成するので、例えば、フレキシブル回路基板やフレキシブル配線板として利用することができる。 According to the method for manufacturing the metal-coated substrate having the eighth configuration, by performing etching on the metal-coated substrate manufactured by the sixth or seventh configuration, a predetermined circuit is formed by the metal film portion. For example, it can be used as a flexible circuit board or a flexible wiring board.
以下、本発明の実施の形態について説明する。
本実施の形態例に係るプラスチックフィルムは、基材の粗化面に接触させることで形成したプラスチックフィルムであり、金属被覆基板は、当該プラスチックフィルムの粗化面に気相法により金属膜を被覆し、所望により該金属膜の上へ更にメッキ法により金属薄膜を積層形成したものである。
Hereinafter, embodiments of the present invention will be described.
The plastic film according to this embodiment is a plastic film formed by bringing it into contact with the roughened surface of the base material, and the metal-coated substrate is coated with a metal film on the roughened surface of the plastic film by a vapor phase method. If desired, a metal thin film is laminated on the metal film by plating.
実施形態に係るプラスチックフィルムを得るには、まず、表面平均粗さＲａが０．０５μm以上であり、表面平均粗さＲａと最大凹凸高さＲｙとの比Ｒｙ／Ｒａが４０以下である粗化面を有する基材を用意する。 In order to obtain the plastic film according to the embodiment, first, the surface roughness Ra is 0.05 μm or more, and the ratio Ry / Ra between the surface average roughness Ra and the maximum unevenness height Ry is 40 or less. A substrate having a surface is prepared.
このような粗さの粗化面を有する基材の製法としては、上記表面粗さの範囲を創出できる方法であれば、どのような方法を用いても良いが、例えば、基材である金属表面に高電流密度のメッキをおこない、所謂「ヤケたメッキ条件」として、粗い金属粒を付加した基材や、基材である金属表面を機械研磨により所定の粗さに荒らした基材を用いることができる。基材の形状としては、プラスチックフィルムを形成できる形状であれば、例えば、板状やロール状（楕円ロール状も可）などいずれの形状であっても良い。 Any method may be used as a method for producing a substrate having such a roughened surface as long as the method can create the above-described surface roughness range. For example, a metal that is a substrate is used. The surface is plated with high current density, and as a so-called “burnt plating condition”, a base material to which rough metal particles are added or a base material whose surface is roughened to a predetermined roughness by mechanical polishing is used. be able to. The shape of the substrate may be any shape such as a plate shape or a roll shape (or an elliptical roll shape is acceptable) as long as it can form a plastic film.
そして、このように粗化面化した基材の粗化面にプラスチックフィルムの前駆体を塗布して、粗化面化処理面を有するプラスチックフィルムを作製する。例えば、プラスチックフィルムとしてポリイミドフィルムを用いる場合は、基材の粗化面に、ポリアミド酸を塗布し、これを加熱イミド化しながら、基材から順次フィルムを引き剥がしたり、特にポリアミド酸をゲルフィルム化してなるポリイミドフィルム前駆体をロール形状の基材の間を押し出したりすことにより、基材の粗化面をフィルムに転写して、粗化面を有するプラスチックフィルムを作製する。 And the precursor of a plastic film is apply | coated to the roughened surface of the base material roughened in this way, and the plastic film which has a roughened surface-treated surface is produced. For example, when a polyimide film is used as a plastic film, polyamic acid is applied to the roughened surface of the base material, and the film is sequentially peeled off from the base material while heating and imidizing it, and in particular, the polyamic acid is converted into a gel film. The polyimide film precursor thus formed is extruded between roll-shaped substrates, whereby the roughened surface of the substrate is transferred to the film to produce a plastic film having the roughened surface.
また、両面が粗化面化されたプラスチックフィルムを所望する場合は、まず第１の粗化面化した基材にプラスチックの前駆体を塗布し、第２の粗化面化した基材で該プラスチックの前駆体を挟み込む。このとき第１および第２の粗化面化した基材の間隔をプラスチックフィルムの所望の厚さと一致させる。挟み込みが完了したら、熱的および／または化学的処理により該プラスチックの前駆体を重合させた後に、両基材を適宜な方法で取り外すことで、両面が粗化面化されたプラスチックフィルムを得ることができる。 When a plastic film having both surfaces roughened is desired, a plastic precursor is first applied to the first roughened substrate, and the second roughened substrate is used to apply the plastic precursor. Insert the plastic precursor. At this time, the distance between the first and second roughened substrates is matched with the desired thickness of the plastic film. When the sandwiching is completed, the plastic precursor is polymerized by thermal and / or chemical treatment, and then both base materials are removed by an appropriate method to obtain a plastic film having both surfaces roughened. Can do.
あるいは、まずプラスチックの前駆体をゲルフィルム化した後、該ゲルフィルムを第１および第２の粗化面化した基材で挟み込む。次に、該両基材の間隔をプラスチックフィルムの所望の厚さと一致させ、熱的および／または化学的処理により該プラスチックの前駆体を重合させた後に、両基材を適宜な方法で取り外すことで、両面が粗化面化されたプラスチックフィルムを得ることとしても良い。 Alternatively, the plastic precursor is first formed into a gel film, and then the gel film is sandwiched between the first and second roughened substrates. Next, after aligning the distance between the two substrates with the desired thickness of the plastic film and polymerizing the precursor of the plastic by thermal and / or chemical treatment, the two substrates are removed by an appropriate method. Thus, a plastic film having roughened surfaces on both sides may be obtained.
また、異なる、粗化面化プラスチックフィルムの製法として、金属の表面に電解メッキ法などで金属粒を付与して、表面平均粗さＲａが０．０５μm以上であり、表面平均粗さＲａと最大凹凸高さＲｙとの比Ｒｙ／Ｒａが４０以下である粗化面化した金属箔を基材として用意し、この金属箔上に硬化前の前駆体を塗布して、その後硬化させたり、この金属箔に硬化前の前駆体を積層し、加熱ラミネート化させたりして、前駆体を硬化し、その後、この金属箔をエッチング除去することで、粗化面を有するプラスチックフィルムを製造する方法も採ることができる。 Further, as a method for producing a different roughened plastic film, metal particles are applied to a metal surface by an electrolytic plating method or the like, and the surface average roughness Ra is 0.05 μm or more, and the surface average roughness Ra is the maximum. A roughened metal foil having a ratio Ry / Ra with the unevenness height Ry of 40 or less is prepared as a base material, and a precursor before curing is applied on the metal foil and then cured, There is also a method for producing a plastic film having a roughened surface by laminating a precursor before curing on a metal foil, laminating by heating, curing the precursor, and then etching away the metal foil. Can be taken.
上述の粗化面化を行った結果、表面平均粗さＲaが０．０９μm以上であり、表面平均粗さＲaと最大凹凸高さＲｙとの比Ｒｙ/Ｒaが40以下である粗化面を有するプラスチックフィルムを得ることができた。そして、当該粗化面上に、金属膜として例えば銅の膜を被覆した場合、銅張り絶縁基板として求められる密着性を確保することができた。また、携帯電話の屈曲部などの、屈曲特性に高い信頼性が求められる用途向けとして、後述する密着性試験おいて１．０Ｎ／ｍｍ２以上の熱安定的な密着強度を得る必要がある場合には、平均粗さＲaを０．２μｍ以上とするのが望ましいことも判明した。 As a result of the above roughening, a roughened surface having a surface average roughness Ra of 0.09 μm or more and a ratio Ry / Ra between the surface average roughness Ra and the maximum unevenness height Ry of 40 or less is obtained. It was possible to obtain a plastic film having the same. And when the copper film | membrane was coat | covered as a metal film on the said roughening surface, the adhesiveness calculated | required as a copper-clad insulating board was able to be ensured. Also, for applications that require high reliability in bending properties, such as bending portions of mobile phones, it is necessary to obtain a heat-stable adhesion strength of 1.0 N / mm 2 or more in an adhesion test described later. It has also been found that the average roughness Ra is preferably 0.2 μm or more.
次に、このようにして得た粗化面を有するプラスチックフィルムの粗化面に金属を被覆することにより、特に高温密着性の高い金属被覆基板を得ることができる。
これは、プラスチックフィルムの形成時に、所定の粗化面を有する基材上でプラスチックフィルムを形成することで表面を粗化面化した場合には、深い凹と高い凸とを有する凹凸が寡占的に存在しているのではなく、比較的凹凸が緩やかで均一な凹凸面が形成され、プラズマ処理による粗化面化とは異なって、表面粗さによるアンカー効果が著しく向上する為と考えられる。
Next, a metal-coated substrate having particularly high high-temperature adhesion can be obtained by coating a metal on the roughened surface of the plastic film having the roughened surface thus obtained.
This is because, when a plastic film is formed on a base material having a predetermined roughened surface and the surface is roughened, unevenness with deep concaves and high convexes is oligopolistic. This is probably because a uniform uneven surface with relatively gentle irregularities is formed, and the anchor effect due to the surface roughness is remarkably improved, unlike the roughened surface by plasma treatment.
金属を被覆する方法としては、気相法、液相法、無電解メッキ法、およびこれらを複合した手法など、いずれの手法も用いることができるが、屈曲の繰り返しに対する耐久性や、はんだ処理などに対する高い耐熱性が必要な用途向けには、これらのうち、気相法の一つであるスパッタ法を第１層目に行うことで、高い密着性が得られることから最も望ましい。 As a method of coating the metal, any method such as a gas phase method, a liquid phase method, an electroless plating method, and a method combining these can be used, but durability against repeated bending, soldering, etc. Among these, for the applications that require high heat resistance, it is most desirable to perform sputtering on the first layer, which is one of the vapor phase methods, because high adhesion can be obtained.
そして、スパッタ法で第１層（シード層）目を形成した後、更に電解ないし無電解のメッキ法で、所定の厚さまで金属膜を成膜する手法を採ることにより、生産性良く、金属膜を被覆することが可能となる。 Then, after forming the first layer (seed layer) by sputtering, the metal film is formed to a predetermined thickness by electrolytic or electroless plating. Can be coated.
なお、必要に応じて、第１層成膜前の前処理として、予めプラスチックフィルムにコロナ放電やグロー放電等の放電処理を施して、フィルム表面に官能基を付加すると、密着強度をより高めることができ好ましい。 In addition, if necessary, as a pretreatment before the first layer film formation, if a plastic film is previously subjected to a discharge treatment such as corona discharge or glow discharge to add a functional group to the film surface, the adhesion strength is further increased. Is preferable.
粗化面化したプラスチックフィルム上に被覆する金属としては、価格や加工性などの点から銅ないし銅を主相とする燐青銅、黄銅等の耐酸化性合金等が望ましく、この他にも例えば、Ａｌ、ステンレスなども使用できるが、これらに限定されるものではない。 The metal to be coated on the roughened plastic film is preferably an oxidation resistant alloy such as phosphor bronze or brass mainly composed of copper or copper from the viewpoint of price and workability. Al, stainless steel, etc. can also be used, but are not limited thereto.
また、プラスチックフィルム上に被覆する第１層目の最初の金属としては、たとえば、Ｃｒ、Ｎｉ、Ｍｏ、Ｗ、Ｖ、Ｔｉ、Ｓｉ、Ｆｅ、Ａｌや、これらを主とする合金を使用するのが好ましい。 Moreover, as the first metal of the first layer to be coated on the plastic film, for example, Cr, Ni, Mo, W, V, Ti, Si, Fe, Al, or an alloy mainly composed of these is used. Is preferred.
この場合、まず、これらの第１層目の最初の金属をシード層として薄く被覆し、その後に、当該最初の金属上へ、銅ないし銅を主相とする燐青銅、黄銅等の耐酸化性合金等を、第２番目の金属として被覆する。この構成を採ると、密着力の高温安定性を更に向上させることができる。ここで、後工程である回路形成の際のエッチング性を良好にするために、第１層目の金属の厚さは、おおよそ１０〜５００Åの範囲に設定するのが望ましく、さらに望ましい範囲は４０〜６０Åである。当該第１層目の第２番目の金属である銅層ないし銅を主相とする耐酸化性合金層の膜厚は、１０００Å以上に設定するのが望ましいが、生産性の観点からは１０００〜３０００Åの範囲がさらに望ましい。 In this case, first, the first metal of the first layer is thinly coated as a seed layer, and then oxidation resistance such as phosphor bronze or brass having copper or copper as a main phase is formed on the first metal. An alloy or the like is coated as the second metal. By adopting this configuration, the high temperature stability of the adhesion can be further improved. Here, in order to improve the etching property at the time of circuit formation, which is a subsequent process, the thickness of the first layer metal is desirably set in a range of approximately 10 to 500 mm, and a more desirable range is 40. ~ 60cm. The film thickness of the first layer of the second metal, the copper layer or the oxidation-resistant alloy layer containing copper as the main phase, is preferably set to 1000 mm or more. The range of 3000 mm is more desirable.
上述したように、プラスチックフィルム上へ第１層目の最初の金属、銅層ないし銅を主相とする耐酸化性合金層等を、スパッタ法等を用いて設けた後に、この層の上へ更にメッキ法等にて所定（例えば、銅または銅合金）の金属膜を被覆する場合、この所定の金属膜の膜厚は、後工程の要求により自在に設定することができる。例えば、当該金属膜に大きな電流を流したいのであれば、数μｍ〜数十μｍとすることもできる。さらに、両面に金属被覆が施された基板を製造する際には、該金属被覆処理を片面ずつ行っても良いし、両面同時に行うこともできる。 As described above, after the first metal of the first layer, the copper layer or the oxidation-resistant alloy layer containing copper as a main phase is provided on the plastic film by using a sputtering method or the like, the layer is formed on this layer. Further, when a predetermined (for example, copper or copper alloy) metal film is coated by a plating method or the like, the film thickness of the predetermined metal film can be freely set according to the requirements of the subsequent process. For example, if a large current is desired to flow through the metal film, the thickness may be several μm to several tens of μm. Furthermore, when manufacturing a substrate having a metal coating on both sides, the metal coating process may be performed on one side at a time or on both sides simultaneously.
プラスチックフィルムとしてポリイミドフィルムを用いる場合は、その前駆体としては、ジアミン成分とテトラカルボン酸二無水物の略等モル量を、有機溶媒中で反応させて作製されたポリアミド酸の溶液を用いることが望ましい。 When a polyimide film is used as a plastic film, a polyamic acid solution prepared by reacting an approximately equimolar amount of a diamine component and tetracarboxylic dianhydride in an organic solvent is used as the precursor. desirable.
前記テトラカルボン酸二無水物としては、例えば、ピロメリット酸二無水物、オキシジフタル酸二無水物、ビフェニル−３，４，３’，４’−テトラカルボン酸二無水物、ビフェニル−２，３，３’，４’−テトラカルボン酸二無水物、ベンゾフェノン−３，４，３’，４’−テトラカルボン酸二無水物、ジフェニルスルホン−３，４，３’，４’−テトラカルボン酸二無水物、４，４’−（２，２−ヘキサフルオロイソプロピリデン）ジフタル酸二無水物、ｍ（ｐ）−ターフェニル−３，４，３‘，４’−テトラカルボン酸二無水物、シクロブタン−１，２，３，４−テトラカルボン酸二無水物、１−カルボキシメチル−２，３，５−シクロペンタントリカルボン酸−２，６：３，５−二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、ビス（３，４−ジカルボキシフェニル）エ−テル二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物など、およびこれらから選ばれる２種以上の混合物が好個に使用できるが、これらに限定されるものではない。 Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, oxydiphthalic dianhydride, biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, biphenyl-2,3, 3 ′, 4′-tetracarboxylic dianhydride, benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, m (p) -terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, cyclobutane- 1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, 2,2-bis (3 , 4-Dicarboxyfe Propane) dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,3,6,7-naphthalenetetracarboxylic An acid dianhydride or the like and a mixture of two or more selected from these can be used in an advantageous manner, but are not limited thereto.
また、ジアミン成分としては、例えば、１，４−ジアミノベンゼン、１，３−ジアミノベンゼン、２，４ジアミノトルエン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエ−テル、３，４’−ジアミノジフェニルエ−テル、３，３’−ジメチル−４，４’−ジアミノビフェニル、２，２’−ジメチル−４，４’−ジアミノビフェニル、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、３，７−ジアミノ−ジメチルジベンゾチオフェン−５，５−ジオキシド、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、４，４’−ビス（４−アミノフェニル）スルフィド、４，４’−ビス（４−アミノフェニル）ジフェニルメタン、４，４’−ビス（４−アミノフェニル）ジフェニルエ−テル、４，４’−ビス（４−アミノフェニル）ジフェニルスルホン、４，４’−ビス（４−アミノフェニル）ジフェニルスルフィド、４，４’−ビス（４−アミノフェノキシ）ジフェニルエ−テル、４，４’−ビス（４−アミノフェノキシ）ジフェニルスルホン、４，４’−ビス（４−アミノフェノキシ）ジフェニルスルフィド、４，４’−ビス（４−アミノフェノキシ）ジフェニルメタン、４，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルフィド、４，４’−ジアミノベンズアニリド、１，ｎ−ビス（４−アミノフェノキシ）アルカン（ｎ＝３，４，５）、１，３−ビス（４−アミノフェノキシ）−２，２−ジメチルプロパン、１，２−ビス［２−（４−アミノフェノキシ）エトキシ］エタン、９，９−ビス（４−アミノフェニル）フルオレン、５（６）−アミノ−１−（４−アミノメチル）−１，３，３−トリメチルインダン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ビス（３−アミノフェノキシ）ビフェニル、２，２−ビス（４−アミノフェノキシフェニル）プロパン、２，２−ビス（４−アミノフェニル）プロパン、ビス[４−（４−アミノフェノキシ）フェニル]スルホン、ビス[４−（３−アミノフェノキシ）フェニル]スルホン、２，２−ビス〔４−（アミノフェノキシ）フェニル〕プロパン、２，２−ビス[４−（４−アミノフェノキシ）フェニル]ヘキサフルオロプロパン、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルメタン、４，６−ジヒドロキシ−１，３−フェニレンジアミン、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、３，３’，４，４’−テトラアミノビフェニル、１−アミノ−３−アミノメチル−３，５，５−トリメチルシクロヘキサン、１，３−ビス（３−アミノプロピル）−１，１，３，３−テトラメチルジシロキサン、１，４−ジアミノブタン、１，６−ジアミノヘキサン、１，８−ジアミノオクタン、１，１０−ジアミノデカン、１，１２−ジアミノドデカン、２，２’−ジメトキシ−４，４’−ジアミノベンズアニリド、２−メトキシ−４，４’−ジアミノベンズアニリドなどの芳香族ジアミン、脂肪族ジアミン、キシレンジアミンなど、および、これらから選ばれる２種以上の混合物が好個に使用できるが、これらに限定されるものではない。 Examples of the diamine component include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4 diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4- Aminophenyl) sulfide, 4,4′-bis (4-aminophenyl) diphenylmethane, 4,4′-bis (4-aminophenyl) di Phenyl ether, 4,4′-bis (4-aminophenyl) diphenyl sulfone, 4,4′-bis (4-aminophenyl) diphenyl sulfide, 4,4′-bis (4-aminophenoxy) diphenyl ether 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′-bis (4-aminophenoxy) diphenyl sulfide, 4,4′-bis (4-aminophenoxy) diphenylmethane, 4,4′- Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzanilide, 1, n-bis (4-aminophenoxy) alkane (n = 3,4,5), 1,3-bis ( 4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9 9-bis (4-aminophenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) ) Biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3 -Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] he Xafluoropropane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3, 3 ′, 4,4′-tetraaminobiphenyl, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-bis (3-aminopropyl) -1,1,3,3- Tetramethyldisiloxane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 2,2′-dimethoxy-4,4 Aromatic diamine such as' -diaminobenzanilide, 2-methoxy-4,4'-diaminobenzanilide, aliphatic diamine, xylenediamine, etc. And mixtures of two or more selected from these can be used in the bang-up, but is not limited thereto.
前記のポリアミド酸製造に使用できる有機溶媒としては、例えば、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホルアミド、Ｎ−メチルカプロラクタム、クレゾ−ル類などが好個に使用できる。これらの有機溶媒は単独で用いてもよく、２種以上を混合して使用してもよいが、これらに限定されるものではない。 Examples of the organic solvent that can be used in the production of the polyamic acid include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, and hexamethylphospho Luamide, N-methylcaprolactam, cresols and the like can be used in a favorable manner. These organic solvents may be used alone or in combination of two or more, but are not limited thereto.
また、閉環剤としては、ジカルボン酸無水物や、２種以上のジカルボン酸無水物の混合物、トリメチルアミン、トリエチルアミン等の脂肪族第３級アミン、およびイソキノリン、ピリジン、ベータピコリン等の複素環式第３級アミンなど、およびこれら脂肪族第３級アミンや複素環式第３級アミンなどの２種以上の混合物を好個に使用することができるが、これらに限定されるものではない。 Examples of the ring-closing agent include dicarboxylic acid anhydrides, mixtures of two or more dicarboxylic acid anhydrides, aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. Secondary amines and the like, and a mixture of two or more of these aliphatic tertiary amines and heterocyclic tertiary amines can be used in an advantageous manner, but are not limited thereto.
また、本願発明に係る金属被覆基板において、被覆金属膜とプラスチックフィルムとの間の線膨張係数差の割合を、±40%以下とすることで、金属被覆時におけるプラスチックフィルムのカールや、該金属被覆基板に熱履歴などを加えた場合の応力を低減できることから、該金属被覆基板の熱安定性が向上でき好ましい。そのような金属膜とプラスチックフィルムとの組み合わせ例として、例えば、金属膜が銅の場合、銅は３００Ｋにおいて16.6×10−6／Ｋの線膨張係数を有するので、プラスチックフィルムは線膨張係数が10〜23×10−６／Ｋのものを選択することが望ましい。さらに、プラスチックフィルムの引っ張り弾性率として、１０００ＭＰａ以上のものを選択することで、高信頼性の金属被覆基板を得ることが出来る。 Further, in the metal-coated substrate according to the present invention, by setting the ratio of the linear expansion coefficient difference between the coated metal film and the plastic film to be ± 40% or less, the curl of the plastic film during metal coating or the metal Since stress when a thermal history is applied to the coated substrate can be reduced, it is preferable because the thermal stability of the metal-coated substrate can be improved. As an example of a combination of such a metal film and a plastic film, for example, when the metal film is copper, since copper has a linear expansion coefficient of 16.6 × 10 −6 / K at 300K, the plastic film has a linear expansion coefficient of 10 It is desirable to select the one of ˜23 × 10 −6 / K. Further, by selecting a plastic film having a tensile modulus of 1000 MPa or more, a highly reliable metal-coated substrate can be obtained.
ここで、引っ張り弾性率が１０００ＭＰａ以上で、線膨張係数が10〜23×10−６／Ｋであるプラスチックフィルムとしてポリイミドフィルムを製造するのに適したジアミン成分とテトラカルボン酸二無水物の組み合わせとしては、例えば、テトラカルボン酸二無水物としてビフェニル−３，４，３’，４’−テトラカルボン酸二無水物、ジアミン成分として１，４−ジアミノベンゼンを主成分としたものを挙げることができる。これらの成分は、何れも各々ジアミン成分とテトラカルボン酸二無水物として５０％以上含まれていることが望ましく、その他の成分は、前述したジアミン成分とテトラカルボン酸二無水物の１種以上と置き換えることができる。 Here, as a combination of a diamine component and a tetracarboxylic dianhydride suitable for producing a polyimide film as a plastic film having a tensile elastic modulus of 1000 MPa or more and a linear expansion coefficient of 10 to 23 × 10 −6 / K. For example, biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride as a tetracarboxylic dianhydride and 1,4-diaminobenzene as a main component as a diamine component can be exemplified. . These components are each desirably contained at least 50% as a diamine component and a tetracarboxylic dianhydride, and the other components are one or more of the diamine component and tetracarboxylic dianhydride described above. Can be replaced.
また、所望により、まずポリアミド酸等を基材に塗布し乾燥させて自己支持性を有するゲルフィルムを作製し、次に、このフィルムの端を固定して縦横に引き延ばすことで、所定の伸延処理を行い、このフィルムの線膨張係数を被覆する金属の線膨張係数に近づけることができる。なお、この処理を行う場合は、まず、表面粗さ（Ｒa）０．０２μｍ以下の平滑な基材上でゲルフィルムを作製し、引き剥がして伸延処理を行い、その後、粗化面化した基材上に押し当てて、触媒法ないしは加熱法およびこれらの複合法でイミド化を行うことが好ましい。 In addition, if desired, first, a polyamic acid or the like is applied to a base material and dried to produce a self-supporting gel film. Next, the end of this film is fixed and stretched vertically and horizontally to obtain a predetermined stretching process. The linear expansion coefficient of the film can be made close to the linear expansion coefficient of the coating metal. In the case of performing this treatment, first, a gel film is prepared on a smooth substrate having a surface roughness (Ra) of 0.02 μm or less, peeled off and subjected to a distraction treatment, and then a roughened surface. It is preferable to imidize by pressing on a material by a catalytic method or a heating method or a composite method thereof.
次に実施形態としての金属被覆基板（銅張りフレキシブル基板）を得るための具体的な製造方法の実施例について、プラスチックフィルムとしてポリイミドフィルムを用いる場合を例として説明する。図１は概略的な工程図であり、図中の工程１０１〜１０５で粗化面を有するプラスチックフィルム１１０を作製し、その上で工程１２１〜１２４を実施することで金属被覆基板１３０を作製し、更にその金属被覆基板に工程１４１を実施することで回路基板１５０を得ることを示している。 Next, a specific example of a manufacturing method for obtaining a metal-coated substrate (copper-clad flexible substrate) as an embodiment will be described using a polyimide film as a plastic film as an example. FIG. 1 is a schematic process diagram. A plastic film 110 having a roughened surface is produced in steps 101 to 105 in the figure, and then a metal-coated substrate 130 is produced by carrying out steps 121 to 124 thereon. Further, it is shown that the circuit board 150 is obtained by performing the step 141 on the metal-coated substrate.
なお、本実施形態において、表面粗さの計測には（株）キーエンス製の超深度形状測定顕微鏡VK-8500を用い、粗化面化フィルム１１０の粗化面において、代表的な部分を測定範囲とし、149×112μｍの範囲を測定レンジ０．０２μmにて白黒超深度で観察した。次に、この測定範囲から任意に20×20μｍの範囲を５点選び、その範囲内の平均粗さＲａ、最大凹凸高さＲｙ、１０点平均粗さＲｚ、二乗平均粗さRsmを各々計測し、その平均値を求め測定値とした。 In this embodiment, the surface roughness is measured using an ultra-deep shape measurement microscope VK-8500 manufactured by Keyence Corporation, and a representative portion of the roughened surface of the roughened film 110 is measured in a measurement range. And a range of 149 × 112 μm was observed at an ultra-deep depth in a measurement range of 0.02 μm. Next, 5 points of 20 × 20 μm are arbitrarily selected from this measurement range, and average roughness Ra, maximum unevenness height Ry, 10-point average roughness Rz, and root mean square roughness Rsm are measured within the range. The average value was obtained and used as the measured value.
（実施例１）
（１）粗化面化基材の製造工程（基材表面粗化面化処理１０１）
二乗平均表面粗さが０．０２μm以下で厚さが０．３ｍｍの銅基板に、下記メッキ液Ａを用いて、電流密度４０Ａ／ｄｍ２で１５秒間通電して成膜することにより、ヤケたニッケル被膜を形成した。次に、同じメッキ液Ａを用いて、電流密度５Ａ／ｄｍ２で５秒間通電し成膜して粗化面化基材を作製した。当該粗化面化基材における表面凹凸の値を、図９に示す。
Example 1
(1) Manufacturing process of roughened surface base material (base surface roughening surface processing 101)
By burning a copper substrate having a mean square surface roughness of 0.02 μm or less and a thickness of 0.3 mm by energizing for 15 seconds at a current density of 40 A / dm 2 using the following plating solution A, the film was burned. A nickel coating was formed. Next, using the same plating solution A, a current was applied at a current density of 5 A / dm 2 for 5 seconds to form a roughened substrate. The value of the surface unevenness in the roughened substrate is shown in FIG.
メッキ液Ａ：スルファミン酸ニッケル Ｎｉ含有率50ｇ/Ｌ
塩化ニッケル Ｎｉ含有率15ｇ/Ｌ
ホウ酸 30ｇ/Ｌ
純水 残部
Plating solution A: Nickel sulfamate Ni content 50g / L
Nickel chloride Ni content 15g / L
Boric acid 30g / L
Pure water balance
（２）ポリイミド前駆体の製造工程（ポリイミド前駆体準備工程１０２）
窒素気流下、重合槽中のN，N−ジメチルアセトアミド１８００ｇへ、１，４−ジアミノベンゼン１０８ｇと、ビフェニル−３，４，３’，４’−テトラカルボン酸二無水物２９４ｇとを添加して撹拌し、ポリアミド酸溶液を作製した。
(2) Production process of polyimide precursor (polyimide precursor preparation process 102)
In a nitrogen stream, 108 g of 1,4-diaminobenzene and 294 g of biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride were added to 1800 g of N, N-dimethylacetamide in the polymerization tank. Stirring to prepare a polyamic acid solution.
（３）粗化面化ポリイミドフィルムの製造工程
前記で作製した粗化面化基材表面にフッ素系離型剤である（有）ブレニー技研製リケイザイＮｏ．１０を塗布、乾燥させた後に、前記で作製したポリアミド酸溶液を塗布流延して（ポリイミド前駆体塗布工程１０３）、１４０℃の熱風で乾燥し、その後、加熱炉内に設置して４８０℃まで段階的に徐々に昇温し、この温度で１分間保持して、溶媒の除去とイミド化を行った（加熱イミド化工程１０４）。
(3) Manufacturing Process of Roughened Surface-Roughened Polyimide Film The surface of the roughened surfaced base material prepared above is a fluorine-based mold release agent. 10 was applied and dried, and then the polyamic acid solution prepared above was applied and cast (polyimide precursor coating step 103), dried with hot air at 140 ° C., and then placed in a heating furnace at 480 ° C. The temperature was gradually raised until the temperature was maintained, and the temperature was maintained at this temperature for 1 minute to remove the solvent and imidize (heating imidization step 104).
次に、このフィルムを基材から引き剥がし、離型材成分をアセトンで洗浄（フィルム引き剥がし・洗浄工程１０５）することで、粗化面を有するポリイミドフィルム（粗化フィルム１１０）を作製した。このポリイミドフィルム（粗化フィルム１１０）の表面凹凸の値を図７に示す。さらに、このポリイミドフィルム（粗化フィルム１１０）において、粗化面の代表的な部分149×112μｍの範囲を、（株）キーエンス製の超深度形状測定顕微鏡VK-8500を用い測定レンジ０．０２μm、白黒超深度で観察した。この観察の結果、得られた顕微鏡写真を図５に示す。また、この観察の結果、図５の顕微鏡写真上にＡ−Ｂで示す線に沿って、111.7μｍの距離に渡り凹凸を計測した。その結果を図６に示す。 Next, this film was peeled off from the base material, and the release material component was washed with acetone (film peeling / washing step 105) to produce a polyimide film (roughened film 110) having a roughened surface. The values of the surface irregularities of this polyimide film (roughened film 110) are shown in FIG. Furthermore, in this polyimide film (roughened film 110), the range of a representative portion 149 × 112 μm of the roughened surface is measured using an ultra-deep shape measuring microscope VK-8500 manufactured by Keyence Corporation, with a measurement range of 0.02 μm, Observed in ultra deep black and white. As a result of this observation, the micrograph obtained is shown in FIG. Further, as a result of this observation, unevenness was measured over a distance of 111.7 μm along the line indicated by AB on the micrograph of FIG. The result is shown in FIG.
（４）スパッタ成膜工程
前記で作製したポリイミドフィルムを１５０℃で２０分間の予備加熱乾燥後、室温に戻し、プラズマエッチング用の真空チャンバ内の陰極に設置した。次に、この真空チャンバ内を１０−４Ｐａまで排気した後、酸素を１０％含むアルゴンガスを導入して、全圧約０．２Ｐａ付近でＡＣ出力１００Ｗを加え、フィルムの粗化面をプラズマエッチングした（エッチング工程１２１）。
(4) Sputter Film Formation Step The polyimide film prepared above was preheated and dried at 150 ° C. for 20 minutes, then returned to room temperature, and placed on the cathode in a vacuum chamber for plasma etching. Next, after evacuating the vacuum chamber to 10 −4 Pa, an argon gas containing 10% oxygen is introduced, an AC output of 100 W is applied at a total pressure of about 0.2 Pa, and the roughened surface of the film is plasma etched. (Etching step 121).
次に、Ｃｒと銅のターゲットが設置されたスパッタ装置内に、前記フィルムの粗化面がターゲット側となるように設置した。次にスパッタ装置の真空チャンバ内を１０−４Ｐａまで排気した後、アルゴンガスを導入して、全圧約０．２Ｐａとし、電力２ｋＷを加えて、Ｃｒ、銅の順にフィルム上に成膜を行った（Ｃｒスパッタ、Ｃｕスパッタ工程１２２、１２３）。ここで、Ｃｒの膜厚は５０Å、銅の膜厚は２０００Åとなるように成膜した。 Next, it was installed in a sputtering apparatus in which a Cr and copper target was installed such that the roughened surface of the film was on the target side. Next, after the vacuum chamber of the sputtering apparatus was evacuated to 10 -4 Pa, argon gas was introduced, and the total pressure of about 0.2 Pa, subjected added power 2 kW, Cr, the deposition on the film in the order of copper (Cr sputtering, Cu sputtering steps 122 and 123). Here, the film thickness of Cr was 50 mm, and the film thickness of copper was 2000 mm.
（５）メッキ成膜工程
上記で作製した銅被膜付きポリイミドフィルム上に、メッキ液として（株）ワールドメタル製、硫酸銅メッキ浴ＢＭＰ−ＣＵＳ（以下、メッキ液Ｂと記載する）を用いて電流密度２Ａ／ｄｍ２で光沢銅被膜を約５μｍメッキ（Ｃｕメッキ工程１２４）し、フィルムと金属膜との密着強度に優れた極薄の 金属被覆基板（銅張りフレキシブル基板）１３０を作製した。
(5) Plating film forming step On the polyimide film with copper coating produced as described above, a current was produced using a copper sulfate plating bath BMP-CUS (hereinafter referred to as plating solution B) manufactured by World Metal Co., Ltd. as a plating solution. A bright copper film having a density of 2 A / dm 2 was plated by about 5 μm (Cu plating step 124), and an ultrathin metal-coated substrate (copper-clad flexible substrate) 130 having excellent adhesion strength between the film and the metal film was produced.
（６）エッチング性評価工程
上記金属被覆基板（銅張りフレキシブル基板）をパターン間隔３０μｍにエッチング加工し（エッチングによる回路形成工程１４１）、それにより得た回路基板１５０へ無電解Ｓｎメッキをおこなった後に、電圧１００Ｖを加えて絶縁抵抗値を測定したところ、１０１１Ω以上の高い絶縁抵抗値が得られた。
(6) Etching property evaluation step After the metal-coated substrate (copper-clad flexible substrate) is etched to a pattern interval of 30 μm (circuit forming step 141 by etching), and electroless Sn plating is performed on the circuit substrate 150 obtained thereby. , the measured insulation resistance value by adding a voltage 100 V, 10 11 Omega more high insulation resistance value is obtained.
（７）密着性評価
密着性の評価は、引き剥がし試験において銅金属膜の強度が必要なため、得られた金属被覆基板（銅張りフレキシブル基板）の銅金属膜の厚さを３０μｍまで厚く再メッキして行った。試験はＪＩＳ Ｃ６４７１の９０゜方向引き剥がし試験に準じ、試料を１８０゜Ｃで加熱処理した後に行った。その結果、１．２〜１．５Ｎ／ｍｍ２と非常に高い密着強度が得られた。
(7) Evaluation of adhesion Since the evaluation of adhesion requires the strength of the copper metal film in the peel test, the thickness of the copper metal film of the obtained metal-coated substrate (copper-clad flexible substrate) is increased to 30 μm. It was done by plating. The test was conducted after heat-treating the sample at 180 ° C. in accordance with the 90 ° peel test of JIS C6471. As a result, a very high adhesion strength of 1.2 to 1.5 N / mm 2 was obtained.
（実施例２）
実施例２では、実施例１における工程（１）において、銅基板として表面を研磨紙により研磨加工したものを用いた。次に、当該銅基板の表面へメッキ液Ａを接触させ、電流密度５Ａ／ｄｍ２で１５秒間通電して、ここへNi膜を成膜し、表面凹凸が図１０のような基材を作製した。さらに、工程（３）で得られるポリイミドフィルムの表面凹凸を図１１のような値とし、他は実施例１と同様にして、金属被覆基板（銅張りフレキシブル基板）を作製した。
(Example 2)
In Example 2, in step (1) in Example 1, the copper substrate whose surface was polished with abrasive paper was used. Next, the plating solution A is brought into contact with the surface of the copper substrate, energized for 15 seconds at a current density of 5 A / dm 2 , a Ni film is formed thereon, and a substrate with surface irregularities as shown in FIG. 10 is produced. did. Furthermore, the surface unevenness | corrugation of the polyimide film obtained at a process (3) was made into the value as FIG. 11, and others carried out similarly to Example 1, and produced the metal-coated board | substrate (copper-clad flexible board | substrate).
エッチング性能および密着性を、実施例１と同様に評価したところ、絶縁抵抗値は１０１１Ω以上、密着強度は０．９〜１．２Ｎ／ｍｍ２と高い値が得られた。 When the etching performance and adhesion were evaluated in the same manner as in Example 1, an insulation resistance value of 10 11 Ω or more and an adhesion strength of 0.9 to 1.2 N / mm 2 were obtained.
（実施例３）
実施例３では、次のように作業を行った。
（１）粗化面化基材の製造工程
平均表面粗さＲａが０．０２μｍのステンレス基板表面へ、下記メッキ液Ｂを接触させて、電流密度２Ａ／ｄｍ２で通電し、光沢銅被膜を１μｍメッキした。次に、当該光沢銅被膜上に前記メッキ液Ａを接触させ、電流密度４０Ａ／ｄｍ２で１５秒間通電することで、ヤケたニッケル被膜を形成し、さらに、再度メッキ液Ａを用いて、電流密度５Ａ／ｄｍ２で１０秒間通電して表面凹凸を有する粗化面化基材を作製した。当該粗化面化基材の表面凹凸は、ほぼ図９の値と同等であった。
Example 3
In Example 3, the operation was performed as follows.
(1) Manufacturing process of roughened surface base material The following plating solution B is brought into contact with the surface of a stainless steel substrate having an average surface roughness Ra of 0.02 μm, and an electric current is applied at a current density of 2 A / dm 2. Plated 1 μm. Next, the plating solution A is brought into contact with the bright copper coating, and a burned nickel coating is formed by energizing for 15 seconds at a current density of 40 A / dm 2. Further, using the plating solution A again, A roughened substrate having surface irregularities was produced by energizing for 10 seconds at a density of 5 A / dm 2 . The surface unevenness of the roughened substrate was substantially the same as that shown in FIG.
（２）ポリイミド前駆体の製造工程
窒素気流下、重合槽中のN，N−ジメチルアセトアミド１８００ｇへ、１，４−ジアミノベンゼン１０８ｇと、ビフェニル−３，４，３’，４’−テトラカルボン酸二無水物２９４ｇとを添加して撹拌し、ポリアミド酸溶液を作製した。
(2) Production process of polyimide precursor To 1,800 g of N, N-dimethylacetamide in a polymerization tank under a nitrogen stream, 108 g of 1,4-diaminobenzene and biphenyl-3,4,3 ′, 4′-tetracarboxylic acid 294 g of dianhydride was added and stirred to prepare a polyamic acid solution.
（３）粗化面化ポリイミドフィルムの製造工程
前記で作製したポリアミド酸溶液を前記で作製した粗化面化基材上に塗布流延して１４０℃の熱風で乾燥し、その後加熱炉内に設置して４８０℃まで段階的に徐々に昇温し、この温度で１分間保持して溶媒の除去とイミド化を行った。
(3) Manufacturing process of roughened polyimide film The polyamic acid solution prepared above is applied and cast onto the roughened surface base material prepared above and dried with hot air at 140 ° C. After installation, the temperature was gradually raised up to 480 ° C. and kept at this temperature for 1 minute to remove the solvent and imidize.
次に、ステンレス基材と銅箔との接合面で、この銅箔付きフィルムを基材から引き剥がし、さらに硝酸水溶液に浸漬することにより銅箔のみを除去して、粗化面を有するポリイミドフィルムを作製した。当該粗化面を有するポリイミドフィルムの表面凹凸は、ほぼ図７の値と同等であった。 Next, a polyimide film having a roughened surface by removing only the copper foil by peeling off the film with the copper foil from the base material at the joining surface of the stainless steel base material and the copper foil, and further immersing in a nitric acid aqueous solution. Was made. The surface irregularities of the polyimide film having the roughened surface were almost the same as the values shown in FIG.
（４）スパッタ成膜工程
前記で作製したポリイミドフィルムを１５０℃で２０分間の予備加熱乾燥後、室温に戻し、プラズマエッチング用の真空チャンバ内の陰極に設置した。次にチャンバ内を１０−４Ｐａまで排気した後、酸素を１０％含むアルゴンガスを導入して、全圧約０．２Ｐａ付近でＡＣ出力１００Ｗを加えてフィルムの粗化面をプラズマエッチングした。
(4) Sputter Film Formation Step The polyimide film prepared above was preheated and dried at 150 ° C. for 20 minutes, then returned to room temperature, and placed on the cathode in a vacuum chamber for plasma etching. Next, after evacuating the chamber to 10 −4 Pa, an argon gas containing 10% oxygen was introduced, and an AC output of 100 W was applied at a total pressure of about 0.2 Pa to plasma etch the roughened surface of the film.
次に、Ｃｒと銅のターゲットが設置されたスパッタ装置内に前記フィルムの粗化面がターゲット側となるように設置した。次に、スパッタ装置のチャンバ内を１０−４Ｐａまで排気した後、アルゴンガスを導入して、全圧約０．２Ｐａとし、電力２ｋＷを加えて、Ｃｒ、銅の順にフィルム上に成膜を行った。ここで、Ｃｒの膜厚は５０Å、銅の膜厚は２０００Åとなるように成膜した。 Next, it was installed in a sputtering apparatus in which a Cr and copper target was installed so that the roughened surface of the film was on the target side. Next, after the inside of the chamber of the sputtering apparatus was evacuated to 10 -4 Pa, argon gas was introduced, and the total pressure of about 0.2 Pa, subjected added power 2 kW, Cr, the deposition on the film in the order of copper It was. Here, the film thickness of Cr was 50 mm, and the film thickness of copper was 2000 mm.
（５）メッキ成膜工程
上記で作製した銅被膜付きポリイミドフィルム上に、前記メッキ液Ｂを用いて電流密度２Ａ／ｄｍ２で光沢銅被膜を約５μｍメッキし、フィルムと金属膜との密着強度に優れた極薄の金属被覆基板（銅張りフレキシブル基板）を作製した。
(5) Plating film formation step On the polyimide film with copper coating prepared above, the plating liquid B is used to plate a bright copper coating with a current density of 2 A / dm 2 at about 5 μm, and the adhesion strength between the film and the metal film An ultra-thin metal-coated substrate (copper-clad flexible substrate) excellent in the above was produced.
（６）エッチング性能評価
上記金属被覆基板（銅張りフレキシブル基板）を実施例１と同様に、パターン間隔３０μｍにエッチング加工し、無電解Ｓｎメッキ後に、電圧１００Ｖを加えて絶縁抵抗値を測定したところ１０１１Ω以上の高い絶縁抵抗値が得られた。
(6) Evaluation of etching performance When the metal-coated substrate (copper-clad flexible substrate) was etched to a pattern interval of 30 μm in the same manner as in Example 1, and after electroless Sn plating, a voltage of 100 V was applied to measure the insulation resistance value. A high insulation resistance value of 10 11 Ω or higher was obtained.
（７）密着性評価
密着性の評価は、引き剥がし試験で銅箔の強度が必要なため、実施例１と同様に、得られた金属被覆基板（銅張りフレキシブル基板）の銅箔の厚さを３０μｍまで厚く再メッキして行った。試験はＪＩＳ Ｃ６４７１の９０゜方向引き剥がし試験に準じて試料を１８０℃で加熱処理した後に行った。その結果、１．２〜１．５Ｎ／ｍｍ２と非常に高い密着強度が得られた。
(7) Adhesion evaluation Since the strength of the copper foil is required in the peeling test for the evaluation of adhesion, the thickness of the copper foil of the obtained metal-coated substrate (copper-clad flexible substrate) is the same as in Example 1. Was re-plated to a thickness of 30 μm. The test was performed after heat-treating the sample at 180 ° C. according to the 90 ° peel test of JIS C6471. As a result, a very high adhesion strength of 1.2 to 1.5 N / mm 2 was obtained.
（比較例１）
実施例１〜３と比較するために比較例に係る金属被覆基板を次の条件で作製した。
即ち、デュポン製ポリイミドフィルム（製品名カプトン）を用いて、酸素分圧２０％の酸素と窒素の混合ガスを用い、ＡＣ出力１００Ｗを加え４０分間プラズマ処理を行い、図８の４０分処理品と同等の表面凹凸を有するポリイミドフィルムを作製した。そして、他は実施例１と同様にして、金属被覆基板（銅張りフレキシブル基板）を作製した。
(Comparative Example 1)
In order to compare with Examples 1-3, the metal-coated board | substrate which concerns on a comparative example was produced on the following conditions.
That is, using a DuPont polyimide film (product name: Kapton), using a mixed gas of oxygen and nitrogen with an oxygen partial pressure of 20%, applying an AC output of 100 W, performing plasma treatment for 40 minutes, A polyimide film having equivalent surface irregularities was produced. Other than that, a metal-coated substrate (copper-clad flexible substrate) was produced in the same manner as in Example 1.
エッチング性能および密着性を実施例１と同様に評価したところ、絶縁抵抗値は１０１０Ω以上と高かったが、密着強度は０．４〜０．７Ｎ／ｍｍ２と低かった。よって、実施例１〜３のように金属被覆基板（銅張りフレキシブル基板）を作製することにより、金属薄膜とプラスチックフィルムとの間に高い密着強度が確保できることが判明した。 When the etching performance and adhesion were evaluated in the same manner as in Example 1, the insulation resistance value was as high as 10 10 Ω or more, but the adhesion strength was as low as 0.4 to 0.7 N / mm 2 . Therefore, it was found that high adhesion strength can be secured between the metal thin film and the plastic film by producing a metal-coated substrate (copper-clad flexible substrate) as in Examples 1 to 3.
本発明の活用例として、様々な実装状況に対応可能なフレキシブル回路基板やフレキシブル配線板へ適用できる。 As an application example of the present invention, the present invention can be applied to a flexible circuit board and a flexible wiring board that can cope with various mounting situations.
１０１ 基材表面粗化処理工程
１０２ ポリイミド前駆体準備工程
１０３ 基材の粗化面にポリイミド前駆体を塗布する工程
１０４ 加熱イミド化工程
１０５ フィルム引き剥がし・洗浄工程
１１０ 粗化フィルム（粗化面を有するプラスチックフィルム）
１２２ Ｃｒスパッタ工程
１２３ Ｃｕスパッタ工程
１２４ Ｃｕメッキ工程
１３０ 金属被覆基板
１４１ エッチングによる回路形成工程
１５０ 回路基板
101 Substrate surface roughening treatment step 102 Polyimide precursor preparation step 103 Step of applying a polyimide precursor to the roughened surface of the substrate 104 Heat imidization step 105 Film peeling / cleaning step 110 Roughened film (Roughened surface) Plastic film)
122 Cr Sputtering Process 123 Cu Sputtering Process 124 Cu Plating Process 130 Metal Coated Substrate 141 Circuit Formation Process by Etching 150 Circuit Board
Claims (8)
該基材表面粗化面化処理工程により得られた基材の粗化面にプラスチックフィルムまたはその前駆体を接触させることにより、前記基材の粗化面に対応した粗化面を有するプラスチックフィルムを形成する粗化面化フィルム形成工程と、を備えることを特徴とするプラスチックフィルムの製造方法。 A substrate surface roughening treatment step for roughening the surface of the substrate;
A plastic film having a roughened surface corresponding to the roughened surface of the substrate by bringing a plastic film or a precursor thereof into contact with the roughened surface of the substrate obtained by the roughened surface of the substrate surface. And a roughened surface-forming film forming step for forming a plastic film.
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| JP2004181187A Pending JP2006001185A (en) | 2004-06-18 | 2004-06-18 | Plastic film, metal-coated substrate, and manufacturing method thereof |
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| JP (1) | JP2006001185A (en) |
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| WO2010073903A1 (en) * | 2008-12-26 | 2010-07-01 | 富士フイルム株式会社 | Surface metal film material, process for producing surface metal film material, process for producing metal pattern material, and metal pattern material |
| KR102197515B1 (en) * | 2019-12-23 | 2021-01-04 | 창 춘 플라스틱스 컴퍼니, 리미티드 | Liquid crystal polymer film and laminate comprising the same |
| US11608410B2 (en) | 2019-12-23 | 2023-03-21 | Chang Chun Plastics Co., Ltd. | Liquid crystal polymer film and laminate comprising the same |
| JP2023550988A (en) * | 2020-11-27 | 2023-12-06 | エルジー イノテック カンパニー リミテッド | Circuit board and its manufacturing method |
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| JP2002060512A (en) * | 2000-08-24 | 2002-02-26 | Du Pont Toray Co Ltd | Roughened aromatic polyimide film and method for producing the same |
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| WO2010073903A1 (en) * | 2008-12-26 | 2010-07-01 | 富士フイルム株式会社 | Surface metal film material, process for producing surface metal film material, process for producing metal pattern material, and metal pattern material |
| KR102197515B1 (en) * | 2019-12-23 | 2021-01-04 | 창 춘 플라스틱스 컴퍼니, 리미티드 | Liquid crystal polymer film and laminate comprising the same |
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| JP2023550988A (en) * | 2020-11-27 | 2023-12-06 | エルジー イノテック カンパニー リミテッド | Circuit board and its manufacturing method |
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