JP2008094923A - Surface modification method of cycloolefin polymer material, surface-modified cycloolefin polymer material obtained using the same, method for forming metallic film on surface-modified cycloolefin polymer material, and cycloolefin polymer material with metallic film - Google Patents
Surface modification method of cycloolefin polymer material, surface-modified cycloolefin polymer material obtained using the same, method for forming metallic film on surface-modified cycloolefin polymer material, and cycloolefin polymer material with metallic film Download PDFInfo
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Abstract
Description
本件発明は、シクロオレフィンポリマー材の表面改質方法、該方法を用いて得られた表面改質シクロオレフィンポリマー材、該表面改質シクロオレフィンポリマー材に金属皮膜を形成する方法及び金属皮膜付シクロオレフィンポリマー材に関する。より具体的には、シクロオレフィンポリマー材表面に形成する金属薄膜層と、シクロオレフィンポリマー材との密着性を向上させる方法と、密着性が良好な金属皮膜を備えるシクロオレフィンポリマー材に関する。 The present invention relates to a surface modification method for a cycloolefin polymer material, a surface modified cycloolefin polymer material obtained by using the method, a method for forming a metal film on the surface modified cycloolefin polymer material, and a cyclohexane with a metal film. The present invention relates to an olefin polymer material. More specifically, the present invention relates to a method for improving adhesion between a metal thin film layer formed on the surface of a cycloolefin polymer material and the cycloolefin polymer material, and a cycloolefin polymer material provided with a metal film having good adhesion.
近年の高度情報化社会への移行により、通信環境が大きく変化している。その中でも、多くの情報量を取り扱うためには光を媒体に使う技術も汎用化している。しかしながら、多くの電子、電気機器内では、まだ電気信号が主要な媒体として使われている。しかし、ＧＨｚ帯の高周波が利用されるようになり、プリント配線板では、信号の高速化、高周波対応のため、低誘電率、低誘電損失（低ｔａｎδ）の特性を有する素材を用いて対応している。そして、高周波信号の伝送特性から、信号伝達回路に必要な導体厚みは薄く、回路端面には良好な直線性が要求されている。更に、クロストークなどのノイズ対策として、信号線にはシールド線を用い、コネクター部分に対してもシールドを施すことが好ましいとの認識も示されている。 With the recent shift to an advanced information society, the communication environment has changed significantly. Among them, in order to handle a large amount of information, a technology that uses light as a medium is also widely used. However, in many electronic and electrical devices, electrical signals are still used as the main medium. However, high-frequency signals in the GHz band have come to be used, and printed wiring boards are made using materials that have low dielectric constant and low dielectric loss (low tan δ) characteristics in order to increase signal speed and support high frequencies. ing. And from the transmission characteristic of a high frequency signal, the conductor thickness required for a signal transmission circuit is thin, and good linearity is required for the circuit end face. Furthermore, it has been shown that it is preferable to use shielded signal lines and shield the connector part as a countermeasure against noise such as crosstalk.
このような、高周波信号の処理に適した素材としては、フッ素樹脂が、優れた電気特性を備えるため、長年用いられてきた。そして、ポリフェニレンエーテル（ＰＰＥ）、ポリフェニレンサルファイド（ＰＰＳ）やシクロオレフィンポリマー（ＣＯＰ）などの、所謂エンジニアリングプラスチックも、高周波特性が良好であるとして提案されている。基本的にこれらの樹脂は、化学的にも熱的にも安定性に優れているものである。従って、プリント配線板用途での使用方法を振り返ってみると、フッ素樹脂では熱可塑性を利用して高温成形するのが一般的である。そして、エンジニアリングプラスチックでは樹脂を変性し、半硬化状態にして、導体金属との接着力を持たせるなどの工夫をして配線板材料としての使用を可能にしている。そして、樹脂表面に金属層を直接形成する技術として、樹脂表面を薬品処理やプラズマ処理により改質した後に無電解めっきしたり、スパッタリング蒸着などの物理蒸着を用いて金属層を形成する方法も提案されている。 As such a material suitable for high-frequency signal processing, a fluororesin has been used for many years because it has excellent electrical characteristics. And so-called engineering plastics such as polyphenylene ether (PPE), polyphenylene sulfide (PPS), and cycloolefin polymer (COP) have been proposed as having good high-frequency characteristics. Basically, these resins are excellent in stability both chemically and thermally. Therefore, looking back at the usage method for printed wiring board applications, fluororesins are generally molded at high temperature using thermoplasticity. In engineering plastics, the resin is modified to be semi-cured so that it can be used as a wiring board material by giving it an adhesive force with the conductor metal. And, as a technique for directly forming a metal layer on the resin surface, a method of forming the metal layer by using electroless plating after modifying the resin surface by chemical treatment or plasma treatment or using physical vapor deposition such as sputtering vapor deposition is also proposed. Has been.
特許文献１には、フッ素樹脂、ポリフェニレン系樹脂やシクロオレフィン系樹脂を用い、高周波信号の処理に対応した多層プリント配線板を作成する技術が開示されている。この技術では、多層プリント配線板の絶縁層構成材料となる樹脂として、熱可塑性樹脂を用いる場合には高温で導体層などを加熱圧着し、熱硬化性樹脂に対しては半硬化状態の樹脂を加圧加熱して硬化反応を進行させ、導体層などを接着している。しかし、この方法では加圧工程を要するため、使用可能な導体層や絶縁層の厚さには限界がある。また、立体形状を備える物体への適用は困難な技術である。 Patent Document 1 discloses a technique for producing a multilayer printed wiring board corresponding to high-frequency signal processing using a fluororesin, a polyphenylene resin, or a cycloolefin resin. In this technology, when a thermoplastic resin is used as the insulating layer constituting material of the multilayer printed wiring board, a conductor layer is heat-pressed at a high temperature, and a semi-cured resin is used for the thermosetting resin. The curing reaction is advanced by heating under pressure, and the conductor layer is adhered. However, since this method requires a pressurizing step, there is a limit to the thickness of the usable conductor layer and insulating layer. Moreover, it is a difficult technique to apply to an object having a three-dimensional shape.
そして、フィルム状のフッ素樹脂表面に金属皮膜を形成する方法として、特許文献２には、フッ素樹脂シート上に密着性が良好な金属皮膜を形成する技術が開示されている。この技術では、フッ素樹脂シートの表面をリモート水素プラズマ処理して親水性を付与し、その後の無電解めっき皮膜との密着性を改善している。 And as a method of forming a metal film on the surface of a film-like fluororesin, Patent Document 2 discloses a technique for forming a metal film with good adhesion on a fluororesin sheet. In this technique, the surface of the fluororesin sheet is subjected to remote hydrogen plasma treatment to impart hydrophilicity, and the adhesion to the subsequent electroless plating film is improved.
また、特許文献３には、フッ素樹脂などの疎水性表面を有する樹脂表面を、まずイオン化した不活性ガスで洗浄し、次いでイオン化された水蒸気を樹脂表面に照射して親水性に改質する技術が開示されている。 Patent Document 3 discloses a technique in which a resin surface having a hydrophobic surface such as a fluororesin is first washed with ionized inert gas, and then ionized water vapor is irradiated onto the resin surface to make it hydrophilic. Is disclosed.
上述のように、電気の不導体である樹脂表面に金属層を形成し、強固な密着強度を得る技術として、化学的に接着力を向上させるため、樹脂の構成を変性物とするか、又は、樹脂表面を改質して親水性表面にする。そして、物理的なアンカー効果による密着性を得るためには、予め、サンドブラストなどにより樹脂表面を粗面化する機械的な加工を施しておく。化学的に接着力を向上させる際は、化学薬品の取り扱いに対し、安全面での配慮が特に強く要求される。また、特許文献３に開示のように、イオン化ガスを用いる手法では設備投資と設備管理の負担が大きい。そして、機械的な加工は、ベースとなる素材に与える歪みが大きくなって用途が限定される。しかも、フィルム状の薄い素材に対しては、前記機械的加工が困難であるという問題がある。 As described above, as a technique for forming a metal layer on the surface of a resin that is an electrical non-conductor and obtaining strong adhesion strength, in order to improve the adhesive force chemically, the resin composition is modified, or The resin surface is modified to a hydrophilic surface. And in order to acquire the adhesiveness by a physical anchor effect, the mechanical process which roughens the resin surface by sandblasting etc. previously is given. When chemically improving the adhesive strength, safety considerations are particularly required for handling chemicals. Moreover, as disclosed in Patent Document 3, the method of using ionized gas has a large burden of equipment investment and equipment management. Further, the mechanical processing is limited in application because the strain applied to the base material increases. Moreover, there is a problem that the mechanical processing is difficult for a thin film-like material.
高周波用電子部品で使用する樹脂として、フッ素樹脂が好ましいものである。しかしながら、特許文献１に開示のように、加熱圧着する手法で製造された銅張積層板は、接着強度を向上させるため、物理的なアンカーが存在している。ところが、このような物理的アンカーが存在すると、次のような問題が発生する。即ち、高周波信号を処理する配線板として使用する際に、高周波信号は、表皮効果により導体の表面側を通ることになる。通常、アンカーは凹凸形状をそなえており、アンカーの存在はクロストークなどノイズの発生原因となっている。一方で、信号の通路として考えれば、その伝達通路である導体厚みは３μｍ〜５μｍで十分であるともいわれている。従って、フィルムや板などの平滑表面に、薄くて平滑な配線を形成することが好ましいのである。 A fluororesin is preferable as the resin used in the high-frequency electronic component. However, as disclosed in Patent Document 1, a copper-clad laminate manufactured by a method of thermocompression bonding has physical anchors for improving the adhesive strength. However, when such a physical anchor exists, the following problems occur. That is, when used as a wiring board for processing a high-frequency signal, the high-frequency signal passes through the surface side of the conductor due to the skin effect. Usually, the anchor has an uneven shape, and the presence of the anchor causes noise such as crosstalk. On the other hand, when considered as a signal path, it is said that a conductor thickness of 3 μm to 5 μm is sufficient. Therefore, it is preferable to form a thin and smooth wiring on a smooth surface such as a film or a plate.
更に、最近の環境意識の高まりを考えると、フッ素樹脂はリサイクルも不可能であり、廃棄物として焼却処理する際には、有害ガスであるフッ化水素が発生する。従って、産業廃棄物としての処理方法は、埋設処理以外に考えられない。従って、電子部品材料などにおいては、フッ素樹脂を極力使用しないことが望ましい。 Furthermore, considering the recent increase in environmental awareness, fluororesins cannot be recycled, and hydrogen fluoride, which is a harmful gas, is generated when incinerated as waste. Therefore, the processing method as industrial waste cannot be considered other than the embedding process. Therefore, it is desirable not to use fluororesin as much as possible in electronic component materials.
従って、フッ素樹脂と同等の電気特性を有する樹脂材料の平滑な表面に、密着性が良好な導電膜を形成する技術に対する要求が存在していたのである。 Therefore, there has been a demand for a technique for forming a conductive film with good adhesion on a smooth surface of a resin material having electrical characteristics equivalent to that of a fluororesin.
そこで、本件発明者等は、上記課題を解決すべく鋭意研究の結果、電気特性がフッ素樹脂に匹敵するシクロオレフィンポリマー材に着目し、その表面改質手法と、該表面改質手法を用いて得られる表面改質シクロオレフィンポリマー材並びに金属被覆シクロオレフィンポリマー材に想到したのである。 Therefore, as a result of intensive research to solve the above problems, the inventors of the present invention have focused on cycloolefin polymer materials whose electrical characteristics are comparable to fluororesin, and using the surface modification method and the surface modification method. The inventors have conceived of the resulting surface-modified cycloolefin polymer material and metal-coated cycloolefin polymer material.
シクロオレフィンポリマー材を構成するシクロオレフィンポリマー樹脂の構造式を、以下の化１に示す。この構造式から、シクロオレフィンポリマー樹脂は、構造的にみて化学的に安定の高い物質であることが判る。そして、シクロオレフィンポリマー材の表面状態のＳＥＭ観察像を図１に示す。この図１から判るように、シクロオレフィンポリマー材の表面は、平滑なものである。以下、上記課題を解決するための手段について述べる。 The structural formula of the cycloolefin polymer resin constituting the cycloolefin polymer material is shown in the following chemical formula 1. From this structural formula, it can be seen that the cycloolefin polymer resin is a substance that is chemically stable in terms of structure. And the SEM observation image of the surface state of a cycloolefin polymer material is shown in FIG. As can be seen from FIG. 1, the surface of the cycloolefin polymer material is smooth. Hereinafter, means for solving the above problems will be described.
本件発明に係るシクロオレフィンポリマー材の表面改質方法： 本件発明に係るシクロオレフィンポリマー材の表面改質方法は、以下の工程Ａ〜工程Ｃを含むことを特徴としている。 Surface Modification Method for Cycloolefin Polymer Material According to the Present Invention: A surface modification method for a cycloolefin polymer material according to the present invention includes the following steps A to C.
工程Ａ：シクロオレフィンポリマー材の表面を脱脂する工程。
工程Ｂ：シクロオレフィンポリマー材に有酸素雰囲気下で紫外線を照射する工程。
工程Ｃ：工程Ｂで得られたシクロオレフィンポリマー材を水洗する工程。
Process A: The process of degreasing the surface of a cycloolefin polymer material.
Step B: A step of irradiating the cycloolefin polymer material with ultraviolet rays in an aerobic atmosphere.
Step C: A step of washing the cycloolefin polymer material obtained in Step B with water.
前記工程Ｂで用いる、紫外線の主波長は１８０ｎｍ〜４００ｎｍであり、シクロオレフィンポリマー材の表面における、紫外線強度は１ｍｗ／ｃｍ２〜５００ｍｗ／ｃｍ２であることが好ましい。 The dominant wavelength of ultraviolet rays used in the step B is 180 nm to 400 nm, and the ultraviolet intensity on the surface of the cycloolefin polymer material is preferably 1 mw / cm 2 to 500 mw / cm 2 .
前記工程Ｂの、紫外線の照射時間は０．５分以上であることが好ましい。 In the step B, the ultraviolet irradiation time is preferably 0.5 minutes or more.
本件発明に係る表面改質シクロオレフィンポリマー材： 本件発明に係る表面改質シクロオレフィンポリマー材は、前記シクロオレフィンポリマー材の表面改質方法を用いて得られたことを特徴としている。 Surface-modified cycloolefin polymer material according to the present invention: The surface-modified cycloolefin polymer material according to the present invention is obtained by using the surface modification method for a cycloolefin polymer material.
本件発明に係る表面改質シクロオレフィンポリマー材の表面に金属皮膜を形成する方法： 本件発明に係る表面改質シクロオレフィンポリマー材の表面に金属皮膜を形成する方法は、以下の工程Ｉ及び工程ＩＩを含むことを特徴としている。 Method for forming a metal film on the surface of the surface-modified cycloolefin polymer material according to the present invention: The method for forming a metal film on the surface of the surface-modified cycloolefin polymer material according to the present invention includes the following steps I and II. It is characterized by including.
工程Ｉ：表面改質シクロオレフィンポリマー材に金属薄膜層を形成する工程。
工程ＩＩ：前記金属薄膜層の上に電解めっきする工程。
Step I: A step of forming a metal thin film layer on the surface-modified cycloolefin polymer material.
Step II: Step of electrolytic plating on the metal thin film layer.
前記工程Ｉは、無電解めっきを用いることが好ましい。 The step I preferably uses electroless plating.
前記工程Ｉは、物理蒸着を用いることが好ましい。 The step I preferably uses physical vapor deposition.
本件発明に係る金属皮膜付シクロオレフィンポリマー材： 本件発明に係る金属皮膜付シクロオレフィンポリマー材は、前記金属皮膜の形成方法を用いて得られた、金属皮膜を備えることを特徴としている。 The cycloolefin polymer material with a metal film according to the present invention: The cycloolefin polymer material with a metal film according to the present invention is characterized by including a metal film obtained by using the method for forming a metal film.
前記金属皮膜付シクロオレフィンポリマー材の、金属皮膜を溶解除去後の表面改質シクロオレフィンポリマー材の表面粗さが、Ｒｚｊｉｓで５μｍ以下であることも好ましい。 It is also preferable that the surface roughness of the surface-modified cycloolefin polymer material after dissolving and removing the metal film of the cycloolefin polymer material with a metal film is 5 μm or less in terms of Rzjis.
本件発明に係るシクロオレフィンポリマー材の改質方法は、有酸素雰囲気下で紫外線を照射する。その結果、シクロオレフィンポリマー材の表面が改質され、表面粗さが小さくても、金属被覆との密着力が良好な表面改質シクロオレフィンポリマー材が得られる。表面改質シクロオレフィンポリマー材の表面には、無電解めっきや物理蒸着での金属薄膜を形成後、必要に応じて電解めっきなどを施すことにより、目的とする用途に最適な金属種で、最適な厚さの金属皮膜を得ることができる。 The method for modifying a cycloolefin polymer material according to the present invention irradiates ultraviolet rays in an aerobic atmosphere. As a result, the surface of the cycloolefin polymer material is modified, and even if the surface roughness is small, a surface modified cycloolefin polymer material having good adhesion to the metal coating can be obtained. The surface of the surface-modified cycloolefin polymer material is formed with a metal thin film by electroless plating or physical vapor deposition, and then subjected to electrolytic plating, etc., if necessary. A metal film having a sufficient thickness can be obtained.
本件発明に係るシクロオレフィンポリマー材の表面改質方法の形態： 本件発明に係るシクロオレフィンポリマー材の表面改質方法は、以下の工程Ａ〜工程Ｃを含んでおり、工程の順に説明する。 Form of surface modification method for cycloolefin polymer material according to the present invention: The surface modification method for a cycloolefin polymer material according to the present invention includes the following steps A to C, and will be described in the order of the steps.
工程Ａは、表面改質の対象とするシクロオレフィンポリマー材の表面に付着した、油脂分などの汚染物質を除去する工程である。例えば、板状のシクロオレフィン材であれば、ラミネート紙などを板材表面の保護材として貼り付けることもあり、ラミネート紙が含む油脂系の成分が板材に付着している。軽微な付着であれば、苛性ソーダ濃度５０ｇ／Ｌ程度のアルカリ水溶液を用いた脱脂処理などを用いる。また、超音波洗浄や、プラズマ洗浄などを用いても良い。しかしながら、この工程Ａは、工程Ｂの前処理として必須とするものではなく、照射した紫外線の照射効果を、確実に活用するためのものである。なお、前記汚染物質量が僅少である場合など、工程Ｂの実施後に工程Ａを実施しても、十分な効果が得られる場合がある。 Step A is a step of removing contaminants such as oil and fat adhering to the surface of the cycloolefin polymer material to be surface-modified. For example, in the case of a plate-like cycloolefin material, laminated paper or the like may be affixed as a protective material on the surface of the plate material, and the oil-based component contained in the laminated paper is attached to the plate material. For slight adhesion, a degreasing treatment using an alkaline aqueous solution having a caustic soda concentration of about 50 g / L is used. Further, ultrasonic cleaning, plasma cleaning, or the like may be used. However, this step A is not indispensable as the pretreatment of the step B, and is for reliably utilizing the irradiation effect of the irradiated ultraviolet rays. In addition, even when the process A is performed after the process B is performed, such as when the amount of the contaminant is very small, a sufficient effect may be obtained.
工程Ｂは、シクロオレフィンポリマー材に有酸素雰囲気下で紫外線を照射する工程である。この工程Ｂで用いる紫外線の主波長は、１８０ｎｍ〜４００ｎｍであり、シクロオレフィンポリマー材の表面における紫外線強度は、１ｍｗ／ｃｍ２〜５００ｍｗ／ｃｍ２であることが好ましい。ここでシクロオレフィンポリマー材の改質に紫外線の照射を用いたのは、有酸素雰囲気下で照射する紫外線エネルギーにより、図２に見られるように、シクロオレフィンポリマー材を構成するＣ−Ｈ結合を、−ＯＨ基及び／又は−Ｃ＝Ｏ基に転化することを目的としている。そして、前記有酸素雰囲気としては、大気雰囲気下での実施が最も簡便であり好ましい。このように、本件発明では有酸素雰囲気下で紫外線を照射することで、Ｃ−Ｈ結合の−ＯＨ基及び／又は−Ｃ＝Ｏ基への転化が容易になる。しかし、例えば、窒素雰囲気やアンモニア雰囲気など、有機高分子を構成しうる元素を含有する雰囲気下で実施すれば、Ｎ等を取り込んだ構造に転化させることも可能である。 Step B is a step of irradiating the cycloolefin polymer material with ultraviolet rays in an aerobic atmosphere. The main wavelength of ultraviolet rays used in this step B is 180 nm to 400 nm, and the ultraviolet intensity on the surface of the cycloolefin polymer material is preferably 1 mw / cm 2 to 500 mw / cm 2 . Here, the ultraviolet irradiation was used for the modification of the cycloolefin polymer material because the C—H bond constituting the cycloolefin polymer material was formed by the ultraviolet energy irradiated in an aerobic atmosphere as shown in FIG. , -OH group and / or -C = O group. And as said aerobic atmosphere, implementation in an air atmosphere is the simplest and preferable. As described above, in the present invention, irradiation with ultraviolet rays in an aerobic atmosphere facilitates conversion of C—H bonds to —OH groups and / or —C═O groups. However, for example, if it is carried out in an atmosphere containing an element that can constitute an organic polymer, such as a nitrogen atmosphere or an ammonia atmosphere, it can be converted into a structure incorporating N or the like.
そして、紫外線の波長の下限を１８０ｎｍとしている。しかし、この波長以下で改質効果が得られないということではなく、一般的に使用可能な波長の下限として設定している。従って、より短波長が得られる光源があれば、より好ましい効果が得られる。そして、上限の波長を４００ｎｍとしたのは、この波長を超える部分では、シクロオレフィンポリマー材の光線透過率が大きくなり、改質効果が得られにくくなるからである。従って、より好ましい紫外線の波長範囲は２００ｎｍ〜３００ｎｍであり、更に好ましい波長範囲は２５０ｎｍ〜２８０ｎｍである。 The lower limit of the wavelength of the ultraviolet light is 180 nm. However, it does not mean that the modification effect cannot be obtained below this wavelength, but is set as the lower limit of the wavelength that can be generally used. Therefore, if there is a light source capable of obtaining a shorter wavelength, a more preferable effect can be obtained. The reason why the upper limit wavelength is set to 400 nm is that the light transmittance of the cycloolefin polymer material increases at a portion exceeding this wavelength, and it becomes difficult to obtain the modification effect. Therefore, a more preferable wavelength range of ultraviolet rays is 200 nm to 300 nm, and a more preferable wavelength range is 250 nm to 280 nm.
そして、照射する紫外線の、シクロオレフィンポリマー材表面における強度については、照射時間との関係を考慮する必要がある。ここで、本件発明において使用する紫外線の強度が１ｍｗ／ｃｍ２未満の場合には、改質に長時間を要して生産効率が悪くなる。一方、紫外線強度が５００ｍｗ／ｃｍ２を超える場合には、紫外線強度が強くなりすぎ、表面だけではなく内部にまで変質が及ぶ場合があり、その制御が困難で、シクロオレフィンポリマー材の全体が脆くなるため、好ましくない。従って、ここに記した上限を超える強度を得ることができる発光源を用いる場合には、紫外線の波長変更への対応と同様、照射時間を変化させるなどにより最適な照射条件を設定する必要があるが、照射時間を極めて短時間にする必要があり、制御が困難となる。 And about the intensity | strength on the cycloolefin polymer material surface of the ultraviolet-ray to irradiate, it is necessary to consider the relationship with irradiation time. Here, when the intensity | strength of the ultraviolet-ray used in this invention is less than 1 mw / cm < 2 >, a long time is required for modification | reformation and production efficiency will worsen. On the other hand, when the ultraviolet intensity exceeds 500 mw / cm 2 , the ultraviolet intensity becomes too strong, and the alteration may extend not only to the surface but also to the inside, which is difficult to control, and the entire cycloolefin polymer material is brittle. Therefore, it is not preferable. Therefore, in the case of using a light source capable of obtaining an intensity exceeding the upper limit described here, it is necessary to set optimum irradiation conditions by changing the irradiation time, as in the case of dealing with a change in the wavelength of ultraviolet rays. However, it is necessary to make the irradiation time extremely short, which makes control difficult.
前記工程Ｂの紫外線の照射時間は０．５分以上を採用する。ここでは下限の照射時間のみを規定し、０．５分としたが、この時間は前記照射する紫外線の強度が、上限である５００ｍｗ／ｃｍ２を想定した設定である。前述したように、紫外線強度と照射時間の設定を変更することにより、表面改質のレベルと、改質の影響が及ぶ表面からの深さをコントロールすることが可能である。 The irradiation time of the ultraviolet ray in the process B is 0.5 minutes or more. Here, only the lower limit of irradiation time is defined and set to 0.5 minutes, but this time is set assuming that the intensity of the irradiated ultraviolet rays is 500 mw / cm 2 which is the upper limit. As described above, it is possible to control the level of the surface modification and the depth from the surface affected by the modification by changing the settings of the ultraviolet intensity and the irradiation time.
工程Ｃは、工程Ｂで得られたシクロオレフィンポリマー材を水洗する工程である。紫外線照射が完了したシクロオレフィンポリマー材は、表面を水洗などにより洗浄する。その後、すぐに金属皮膜形成工程に投入するのであれば、乾燥しなくても構わない。しかし、金属皮膜の形成を数日後に実施する場合などには、乾燥しておくことにより表面ムラの影響を小さくできる。そして、前述のように、脱脂を行わずに紫外線を照射する場合には、水洗工程の前に脱脂工程を設け、洗浄化を図ることがことが、後の金属皮膜の形成安定性の観点から好ましい。従って、乾燥するか否かは、次工程を施すまでの時間によって任意に判断すればよい。 Step C is a step of washing the cycloolefin polymer material obtained in Step B with water. The surface of the cycloolefin polymer material that has been irradiated with ultraviolet rays is washed with water. Thereafter, if it is immediately put into the metal film forming step, it does not have to be dried. However, when the metal film is formed after several days, the influence of surface unevenness can be reduced by drying. And, as described above, in the case of irradiating ultraviolet rays without degreasing, it is possible to provide a degreasing step before the water washing step and to perform cleaning from the viewpoint of the stability of the formation of the subsequent metal film. preferable. Accordingly, whether or not to dry may be arbitrarily determined depending on the time until the next step is performed.
本件発明に係る表面改質シクロオレフィンポリマー材の形態： 本件発明に係る表面改質シクロオレフィンポリマー材は、上記シクロオレフィンポリマー材の表面改質方法を施したシクロオレフィンポリマー材である。従って、最終用途の要求特性に応じて、紫外線照射条件を設定して改質処理されており、改質後の表面には、改質前には存在していなかった−ＯＨ基や−Ｃ＝Ｏ基が形成されている。これらの−ＯＨ基や−Ｃ＝Ｏ基が形成されていることで、化学的接着力が向上するのである。また、改質後の表面形状は、図３に見られるように、平滑表面が蝕刻された形状になっており、蝕刻部分は直径が０．１μｍ〜２０μｍ、深さは０．１μｍ〜５μｍ程度であり、表面粗さも、平滑な被覆金属との界面を得るためには最適な状態となっている。 Form of surface-modified cycloolefin polymer material according to the present invention: The surface-modified cycloolefin polymer material according to the present invention is a cycloolefin polymer material that has been subjected to the surface modification method for the cycloolefin polymer material. Therefore, in accordance with the required characteristics of the final use, the ultraviolet irradiation conditions are set and the modification treatment is performed. On the surface after the modification, the —OH group or —C═ O groups are formed. The formation of these —OH groups and —C═O groups improves the chemical adhesive force. Moreover, the surface shape after modification is a shape in which a smooth surface is etched as seen in FIG. 3, and the etched portion has a diameter of about 0.1 μm to 20 μm and a depth of about 0.1 μm to 5 μm. The surface roughness is also in an optimum state for obtaining a smooth interface with the coated metal.
本件発明に係る表面改質シクロオレフィンポリマー材の表面に金属皮膜を形成する方法の形態： 本件発明において、表面改質シクロオレフィンポリマー材表面に金属皮膜を形成する方法は、以下の工程Ｉ及び工程ＩＩを含んでいる。一般的には、金属皮膜を形成する場合、電解めっきを採用することが、生産性も良好で、品質も安定する。しかしながら、非導電体に金属皮膜を形成しようとすると、当初は、電解めっきに必要な電気量を供給する金属薄膜が存在していない。従って、表面改質シクロオレフィンポリマー材表面に、一旦薄く金属層を形成する必要がある。また、要求品質に適合さえすれば、例えば高速無電解めっきで所望の厚さの金属皮膜にすることもできる。 Form of Method for Forming Metal Film on Surface of Surface-Modified Cycloolefin Polymer Material According to the Present Invention: In the present invention, the method for forming a metal film on the surface of the surface-modified cycloolefin polymer material includes the following steps I and II is included. In general, when forming a metal film, it is preferable to employ electrolytic plating to improve productivity and stabilize quality. However, when attempting to form a metal film on a non-conductor, initially there is no metal thin film that supplies the amount of electricity necessary for electrolytic plating. Therefore, it is necessary to form a thin metal layer once on the surface of the surface-modified cycloolefin polymer material. Further, as long as the required quality is met, a metal film having a desired thickness can be formed by, for example, high-speed electroless plating.
工程Ｉは、表面改質シクロオレフィンポリマー材に金属薄膜層を形成する工程である。ここでは、無電解めっきを用いることが好ましい。本件発明に係るシクロオレフィンポリマー材の表面は、図３に明らかなように、部分的に蝕刻されたような形状を示しており、その表面には−ＯＨ基や−Ｃ＝Ｏ基が形成されている。従って、液相反応を用いることにより、析出する金属成分と表面改質シクロオレフィンポリマー材との間の化学結合が容易になる。また、液の蝕刻形状内への浸み込みによって、狭隘な部分にまで金属成分を析出させて金属層を形成することができ、極めて微視的なアンカー効果を得て、シクロオレフィンポリマー材と金属皮膜との密着性を良好にする。そして、ここで用いる無電解めっきは、前述のように高速無電解めっき浴を用い、所望の厚さまでめっきアップしても構わないが、析出した無電解めっき層と表面改質シクロオレフィンポリマー材と密着性の安定化を図る場合には、ホルマリン系無電解めっき浴又は析出速度の遅い次亜リン酸を還元剤として用いた無電解めっき浴を採用することが好ましい。極めて微細な凹凸形状の狭隘部分への金属成分の析出精度が向上して、無電解めっき層と表面改質シクロオレフィンポリマー材との良好な密着性が得られるからである。 Step I is a step of forming a metal thin film layer on the surface-modified cycloolefin polymer material. Here, it is preferable to use electroless plating. As shown in FIG. 3, the surface of the cycloolefin polymer material according to the present invention shows a partially etched shape, and —OH groups and —C═O groups are formed on the surface. ing. Therefore, the chemical bond between the deposited metal component and the surface-modified cycloolefin polymer material is facilitated by using the liquid phase reaction. Also, by immersing the liquid into the etched shape, it is possible to deposit a metal component to a narrow portion to form a metal layer, and to obtain a very microscopic anchor effect, Improves adhesion to the metal film. The electroless plating used here may be plated up to a desired thickness using a high-speed electroless plating bath as described above, but the deposited electroless plating layer, surface modified cycloolefin polymer material, In order to stabilize the adhesion, it is preferable to employ a formalin electroless plating bath or an electroless plating bath using hypophosphorous acid having a slow deposition rate as a reducing agent. This is because the deposition accuracy of the metal component on the narrow portion of the extremely fine uneven shape is improved, and good adhesion between the electroless plating layer and the surface-modified cycloolefin polymer material can be obtained.
また、前記工程Ｉの金属薄膜層の形成には、物理蒸着法を用いることもできる。この物理蒸着法は、表面改質が施されていないプラスチック材などの表面に、金属やセラミックなどの皮膜を形成することもできる。かかる場合、プラスチック材に表面改質を行わなくても、当該プラスチック材表面に物理蒸着法で形成した金属薄膜層は、ある程度の密着強度を示す。しかしながら、加熱処理や冷熱サイクル等の熱衝撃を受けた場合には、部分的に剥離する等の密着不良部分が発生する。従って、上述の表面改質シクロオレフィンポリマー材を用い、その表面にスパッタリング蒸着などの物理蒸着法で金属薄膜層を形成すると、熱衝撃を受けても、当該金属薄膜層が剥離しにくくなる。 Moreover, physical vapor deposition can also be used for formation of the metal thin film layer of the said process I. This physical vapor deposition method can also form a film of metal or ceramic on the surface of a plastic material or the like that has not been subjected to surface modification. In such a case, the metal thin film layer formed on the surface of the plastic material by physical vapor deposition exhibits a certain degree of adhesion strength without performing surface modification on the plastic material. However, when subjected to a thermal shock such as heat treatment or a cooling / heating cycle, a poor adhesion portion such as partial peeling occurs. Therefore, when the above-described surface-modified cycloolefin polymer material is used and a metal thin film layer is formed on the surface by a physical vapor deposition method such as sputtering vapor deposition, the metal thin film layer is difficult to peel off even when subjected to thermal shock.
上記無電解めっきには、無電解銅めっき、無電解ニッケルめっき、無電解スズめっき、無電解金めっき等を用いることができる。そして、この無電解めっき層又は物理蒸着法で形成する金属薄膜層は、０．１μｍ〜３μｍの厚さとすることが好ましい。金属薄膜層の厚さが０．１μｍ未満の場合には、膜圧の均一性に欠け、電気メッキを施すときの安定した通電状態が得られない。これに対し、金属薄膜層の厚さが３μｍを超えても、膜厚の均一性が向上するわけではなく、むしろ析出した金属表面が粗れてきて、その後の電解めっきで形成する電解めっき層の表面が粗れる結果となる。そして、平坦且つ膜厚均一性に優れ、後の電解めっきに悪影響を与えない金属薄膜層を安定して得る観点から、金属薄膜層を０．５μｍ〜２μｍの厚さとすることが、より好ましい。 For the electroless plating, electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating, or the like can be used. And it is preferable that the metal thin film layer formed by this electroless-plating layer or the physical vapor deposition method shall be 0.1 micrometer-3 micrometers in thickness. When the thickness of the metal thin film layer is less than 0.1 μm, the film pressure is not uniform and a stable energization state cannot be obtained when electroplating is performed. On the other hand, even if the thickness of the metal thin film layer exceeds 3 μm, the uniformity of the film thickness is not improved, but rather the deposited metal surface becomes rough and the electrolytic plating layer formed by the subsequent electrolytic plating This results in a rough surface. From the viewpoint of stably obtaining a metal thin film layer that is flat and excellent in film thickness uniformity and does not adversely affect the subsequent electroplating, it is more preferable that the metal thin film layer has a thickness of 0.5 μm to 2 μm.
工程ＩＩ：前記金属薄膜層の上に電解めっきして、表面改質シクロオレフィンポリマー材表面に金属被膜を形成する工程である。ここで言う、電解めっきには、特段の限定はない。ここで形成する電解めっき層の厚さに関しても特段の限定はない。得られる金属皮膜付シクロオレフィンポリマー材の用途に応じて、任意の材質、厚さを選択すればよいのである。また、電解めっき層の材質に関してもである。例えば、銅メッキ、ニッケルめっき、スズめっき、亜鉛めっき、鉄めっき、銅−亜鉛合金めっき、ニッケル−コバルト合金めっき、ニッケル−亜鉛合金めっき等種々の電解めっきの採用が可能である。更に、念のために記載しておくが、ここで言う電解めっきで形成する電解めっき層の材質と、前記金属薄膜層を構成する金属成分とは、同一材質でも異種材質であっても構わない。この組み合わせも、金属皮膜付シクロオレフィンポリマー材の用途、要求する表面改質シクロオレフィンポリマー材表面と金属被膜との間の密着性レベル等に応じて任意に選択すればよい。 Step II: A step of forming a metal film on the surface of the surface-modified cycloolefin polymer material by electrolytic plating on the metal thin film layer. Here, there is no particular limitation on the electrolytic plating. There is no special limitation also about the thickness of the electroplating layer formed here. Any material and thickness may be selected according to the use of the resulting cycloolefin polymer material with a metal film. It is also about the material of an electroplating layer. For example, various types of electrolytic plating such as copper plating, nickel plating, tin plating, zinc plating, iron plating, copper-zinc alloy plating, nickel-cobalt alloy plating, and nickel-zinc alloy plating can be employed. In addition, as described just in case, the material of the electroplating layer formed by electroplating and the metal component constituting the metal thin film layer may be the same material or different materials. . This combination may also be arbitrarily selected according to the use of the cycloolefin polymer material with a metal film, the level of adhesion between the surface-modified cycloolefin polymer material surface and the metal film to be required, and the like.
本件発明に係る金属皮膜付シクロオレフィンポリマー材の形態： 本件発明に係る金属皮膜付シクロオレフィンポリマー材は、前記金属皮膜の形成方法を用いて得られた、金属皮膜を備える金属皮膜付シクロオレフィンポリマー材である。ここで、上述の表面改質シクロオレフィンポリマー材表面への金属被膜の形成方法の説明から理解できるため、金属被膜の厚さ、材質等に関する説明は省略する。 Form of cycloolefin polymer material with metal film according to the present invention: The cycloolefin polymer material with metal film according to the present invention is a cycloolefin polymer with metal film, which is obtained by using the method for forming a metal film. It is a material. Here, since it can be understood from the description of the method for forming the metal film on the surface of the surface-modified cycloolefin polymer material, description on the thickness, material, etc. of the metal film is omitted.
ここで言う金属皮膜付シクロオレフィンポリマー材は、シクロオレフィンポリマー材と金属皮膜との密着性に優れ、耐熱性なども良好である。従って、種々の装飾めっき、電子材料用途等での使用が可能である。例えば、シクロオレフィンポリマーを基材として用いた自動車用部品表面への金属光沢めっき、シクロオレフィンポリマーを絶縁層に用いた配線板等である。特に、プリント配線板材料として用いる事が好適である。本件発明に係る金属皮膜付シクロオレフィンポリマー材は、電気的絶縁性に優れ、金属皮膜とシクロオレフィンポリマー材との界面が平坦であるため、ファインピッチ回路及びエッチングファクターに優れた回路の形成能に優れる。そして、高周波特性に優れるため、フッ素樹脂基板の代替としての使用が可能で、軽量化とコストダウンとが達成できる。また、薄いシクロオレフィンポリマーフィルムの両面に金属皮膜を形成すれば、プリント配線板の内蔵キャパシタを形成するための材料とできる。更に、電気抵抗値の大きな金属成分で金属皮膜を形成すれば、抵抗回路の形成が可能な導電層となる。以上に述べてきたプリント配線板製造の場で、本件発明に係る金属皮膜付シクロオレフィンポリマー材を用いると、あらゆる意味において、回路設計時に要求される特性値のバラツキを小さくできる。 The cycloolefin polymer material with a metal film said here is excellent in the adhesiveness of a cycloolefin polymer material and a metal film, and its heat resistance is also good. Therefore, it can be used in various decorative plating and electronic material applications. For example, it is metallic luster plating on the surface of automotive parts using a cycloolefin polymer as a base material, and a wiring board using a cycloolefin polymer as an insulating layer. In particular, it is suitable to use as a printed wiring board material. The cycloolefin polymer material with a metal film according to the present invention is excellent in electrical insulation and has a flat interface between the metal film and the cycloolefin polymer material. Excellent. And since it is excellent in a high frequency characteristic, it can be used as a substitute for a fluororesin substrate, and weight reduction and cost reduction can be achieved. Moreover, if a metal film is formed on both surfaces of a thin cycloolefin polymer film, it can be used as a material for forming a built-in capacitor of a printed wiring board. Furthermore, if a metal film is formed with a metal component having a large electric resistance value, a conductive layer capable of forming a resistance circuit is obtained. When the cycloolefin polymer material with a metal film according to the present invention is used in the printed wiring board manufacturing process described above, it is possible to reduce variations in characteristic values required at the time of circuit design in any sense.
また、前記金属皮膜付シクロオレフィンポリマー材の金属皮膜を溶解除去した後の表面改質シクロオレフィンポリマー材の表面粗さは、Ｒｚｊｉｓで５μｍ以下であることが好ましい。この表面粗さは、用途に応じて設定するものではあるが、有酸素雰囲気下で紫外線を照射するという改質手法を用いることによって、前述の如く化学的な接着力が有効に作用するため、むやみに粗くする必要がなくなる。その結果、一般的なプリント配線板に用いる銅箔の接着面に求められるベリーロープロファイルレベルが好ましい。そして、プリント配線板に用いて、更に高周波用途での使用を考えると、より好ましい表面粗さ（Ｒｚｊｉｓ）は１μｍ以下である。 The surface roughness of the surface-modified cycloolefin polymer material after dissolving and removing the metal film of the cycloolefin polymer material with a metal film is preferably 5 μm or less in terms of Rzjis. This surface roughness is set according to the application, but by using a modification technique of irradiating ultraviolet rays in an aerobic atmosphere, the chemical adhesive force acts effectively as described above, Eliminates the need for roughing. As a result, the belly low profile level required for the adhesive surface of the copper foil used for a general printed wiring board is preferable. And when it considers the use for a high frequency use further using it for a printed wiring board, a more preferable surface roughness (Rzjis) is 1 micrometer or less.
本実施例では、シクロオレフィンポリマー材として、日本ゼオン株式会社製ゼオネクス４２０の板厚３ｍｍの板材を用い、改質処理の前段では５０ｇ／ＬのＮａＯＨ水溶液に５０℃で２分間浸漬して脱脂した。 In this example, as a cycloolefin polymer material, a ZEONEX 420 made by Nippon Zeon Co., Ltd., having a plate thickness of 3 mm, was degreased by immersing it in a 50 g / L NaOH aqueous solution at 50 ° C. for 2 minutes before the reforming treatment. .
＜表面改質＞
表面改質処理方法として、以下の４種類を比較した。第１は紫外線照射処理、第２はＴＩＯ２を媒介させた紫外線照射処理、第３は酸素プラズマ処理、第４はプリント配線板のスルーホール内壁の処理であるデスミア処理である。それぞれの処理条件を表１に示す。
<Surface modification>
The following four types of surface modification treatment methods were compared. The first is an ultraviolet irradiation treatment, the second is an ultraviolet irradiation treatment mediated by TIO 2 , the third is an oxygen plasma treatment, and the fourth is a desmear treatment which is a treatment of the through-hole inner wall of the printed wiring board. Each processing condition is shown in Table 1.
上記処理後、表面の改質状況を確認するために、試験片表面に水滴を滴下し、接触角を観察して親水性を評価した。親水性を改善できたのは、紫外線照射処理、ＴＩＯ２を媒介させた紫外線照射処理及び酸素プラズマ処理であった。以下、紫外線照射処理した試片をＣＯＰＵ、ＴＩＯ２を媒介させた紫外線照射処理した試片をＣＯＰＴ、酸素プラズマ処理した試片をＣＯＰＯ、デスミア処理した試片をＣＯＰＤと称する。更に、親水性が改善された試片について、赤外分光分析装置（ＦＴ−ＩＲ：株式会社パーキンエルマージャパン製スペクトラムワン）を用い、ＡＴＲ法で表面分析を実施した。その結果、吸収スペクトルの変化が見られたのは、ＣＯＰＵとＣＯＰＴであり、ＣＯＰＵでの吸収スペクトルの変化が、最も顕著であった。上記結果をまとめて表２に示す。また、赤外吸収スペクトルを図２に、ＣＯＰＵ、ＣＯＰＴ及びＣＯＰＯの表面ＳＥＭ観察像を図３〜図５に示す。図２から、紫外線照射した表面には−ＯＨ基や−Ｃ＝Ｏ基が形成されていることが判る。また、図３から、ＣＯＰＵでは表面形状も変化していることが見て取れる。 After the above treatment, in order to confirm the surface modification state, water droplets were dropped on the surface of the test piece, and the contact angle was observed to evaluate the hydrophilicity. The hydrophilicity was improved by ultraviolet irradiation treatment, ultraviolet irradiation treatment mediated by TIO 2 and oxygen plasma treatment. Hereinafter, a specimen subjected to ultraviolet irradiation treatment is referred to as COP U , a specimen subjected to ultraviolet irradiation treatment mediated by TIO 2 is referred to as COP T , a specimen subjected to oxygen plasma treatment is referred to as COP 2 O , and a specimen subjected to desmear treatment is referred to as COP D. Furthermore, the surface analysis was implemented by the ATR method about the test piece by which hydrophilicity was improved using the infrared spectroscopy analyzer (FT-IR: Spectrum One by Perkin-Elmer Japan Co., Ltd.). As a result, the change in the absorption spectrum was observed in COP U and COP T , and the change in the absorption spectrum in COP U was most remarkable. The results are summarized in Table 2. Moreover, an infrared absorption spectrum is shown in FIG. 2, and surface SEM observation images of COP U , COP T and COP O are shown in FIGS. From FIG. 2, it can be seen that —OH groups and —C═O groups are formed on the surface irradiated with ultraviolet rays. Further, it can be seen from FIG. 3 that the surface shape of COP U is also changed.
＜金属薄膜の形成＞
ここでは、表面改質処理で水濡れ性が改善された、ＣＯＰＵ、ＣＯＰＴ及びＣＯＰＯを対象とし、銅皮膜を形成した。銅皮膜の形成フローを表３に示す。
<Formation of metal thin film>
Here, a copper film was formed for COP U , COP T and COP O whose water wettability was improved by the surface modification treatment. The formation flow of the copper film is shown in Table 3.
銅薄膜の形成には無電解めっきを用い、グリオキシル酸浴と、次亜リン酸浴の２種類を用いて、厚さ０．５μｍの無電解銅めっき薄膜を形成した。グリオキシル酸浴の浴組成と処理条件を表４に、次亜リン酸浴の浴組成と処理条件を表５に示す。 Electroless plating was used to form the copper thin film, and an electroless copper plating thin film having a thickness of 0.5 μm was formed using two types of a glyoxylic acid bath and a hypophosphorous acid bath. Table 4 shows the bath composition and treatment conditions of the glyoxylic acid bath, and Table 5 shows the bath composition and treatment conditions of the hypophosphorous acid bath.
この銅薄膜上に、表６に示す組成の硫酸酸性銅めっき液を用い、液温２５℃、電流密度３．３３Ａ／ｄｍ２で電解し、厚さ２０μｍの電解銅皮膜を形成した。 On this copper thin film, the sulfuric acid acidic copper plating solution of the composition shown in Table 6 was electrolyzed at a liquid temperature of 25 ° C. and a current density of 3.33 A / dm 2 to form an electrolytic copper film having a thickness of 20 μm.
＜密着性評価＞
上記にて得られた、銅皮膜付シクロオレフィンポリマー材の皮膜密着性を、テープ試験で評価した。その結果、ＣＯＰＵを用いた試験片では剥離が観察されなかったが、ＣＯＰＴ及びＣＯＰＯを用いた試験片では剥離が観察された。結果を表２に示す。ここで剥離が観察されなかったＣＯＰＵを用いた試験片について、シクロオレフィンポリマー材と銅皮膜との界面の断面観察像を図７に示す。この銅皮膜付シクロオレフィンポリマー材に、プリント配線板の形成に用いる材料としての実用性を評価する目的で、図６に示す配線を形成し、引き剥がし強さを測定した。その結果、無電解銅めっきにグリオキシル酸浴を用いた試験片の引き剥がし強さは５．２９Ｎ／ｃｍ、次亜リン酸浴を用いた試験片の引き剥がし強さは６．７６Ｎ／ｃｍであった。次亜リン酸浴を用いて得られた試験片の、引き剥がし強さ測定後のシクロオレフィンポリマー材表面のＳＥＭ観察像を図８に示す。改質処理後の表面である図３と比較すると、シクロオレフィンポリマー材表面の凹凸形状部分がより広い面積となっている。すなわち、銅配線を引き剥がす際に、シクロオレフィンポリマー材の表面層が、銅配線に付着した状態で引き剥がされていることが明白であり、シクロオレフィンポリマー材と銅皮覆層との密着性が良好であることを示している。
<Adhesion evaluation>
The film adhesion of the cycloolefin polymer material with a copper film obtained above was evaluated by a tape test. As a result, no peeling was observed in the test piece using COP U , but peeling was observed in the test piece using COP T and COP O. The results are shown in Table 2. FIG. 7 shows a cross-sectional observation image of the interface between the cycloolefin polymer material and the copper film for the test piece using COP U in which peeling was not observed. For the purpose of evaluating the practicality as a material used for forming a printed wiring board on this cycloolefin polymer material with a copper film, the wiring shown in FIG. 6 was formed, and the peel strength was measured. As a result, the peel strength of the test piece using the glyoxylic acid bath for electroless copper plating was 5.29 N / cm, and the peel strength of the test piece using the hypophosphorous acid bath was 6.76 N / cm. there were. FIG. 8 shows an SEM observation image of the surface of the cycloolefin polymer material after the peel strength measurement of the test piece obtained using the hypophosphorous acid bath. Compared with FIG. 3 which is the surface after the modification treatment, the uneven shape portion of the cycloolefin polymer material surface has a wider area. That is, when the copper wiring is peeled off, it is clear that the surface layer of the cycloolefin polymer material is peeled off while adhering to the copper wiring, and the adhesion between the cycloolefin polymer material and the copper skin covering layer is clear. Is good.
更に、ＣＯＰＵ について、紫外線照射時間を１０分、２０分、４５分と変更した試片を用い、無電解めっきに次亜リン酸浴を用いて同様の試験片を作成し、引き剥がし強さを評価した。結果は、それぞれ、７．９４Ｎ／ｃｍ、８．０４Ｎ／ｃｍ及び６．０８Ｎ／ｃｍであり、紫外線照射時間が長すぎると、密着力が低下する傾向が見られた。引き剥がし強さの評価結果を表７にまとめて示す。
上述の実施例では、プリント配線板を用途とした板の表面改質と銅皮膜の形成を行って評価したが、本件発明の対象物は、板状の物に限定されないと本件発明者等は考えている。例えば、ビーズ状のシクロオレフィンポリマー材の表面を改質し、表面に金属皮膜を形成すれば、軽量で導電性を有する粉体とできる可能性を有している。この場合には、導電性塗料などのフィラーとして有用となる。 In the above-described embodiment, evaluation was performed by performing surface modification of a board and formation of a copper film for use as a printed wiring board, but the subject matter of the present invention is not limited to a plate-shaped object. thinking. For example, if the surface of a bead-shaped cycloolefin polymer material is modified and a metal film is formed on the surface, there is a possibility that the powder can be made light and conductive. In this case, it is useful as a filler for conductive paints and the like.
本件発明に係るシクロオレフィンポリマー材の改質方法は、有酸素雰囲気下で紫外線を照射する。その結果、シクロオレフィンポリマー材の表面組成と形状が改質され、表面粗さが小さいままで、金属被覆の密着力が良好な、表面改質シクロオレフィンポリマー材が得られる。表面改質シクロオレフィンポリマー材の表面には、無電解めっきや物理蒸着で金属薄膜を形成後、必要に応じて電解めっきなどを施すことができる。表面に銅皮膜を形成した場合には、プリント配線板の形成材料として好適であり、コネクターのケーシングなどの成型品にニッケル層を形成すれば、良好な電磁波シールド効果を有するものとなる。 The method for modifying a cycloolefin polymer material according to the present invention irradiates ultraviolet rays in an aerobic atmosphere. As a result, the surface composition and shape of the cycloolefin polymer material are modified, and a surface-modified cycloolefin polymer material having good surface adhesion and a good metal coating adhesion can be obtained. On the surface of the surface-modified cycloolefin polymer material, after forming a metal thin film by electroless plating or physical vapor deposition, electrolytic plating or the like can be performed as necessary. When a copper film is formed on the surface, it is suitable as a material for forming a printed wiring board. When a nickel layer is formed on a molded product such as a connector casing, a good electromagnetic shielding effect is obtained.
Claims (9)
以下の工程Ａ〜工程Ｃを含むことを特徴とするシクロオレフィンポリマー材の表面改質方法。
工程Ａ：シクロオレフィンポリマー材の表面を脱脂する工程。
工程Ｂ：シクロオレフィンポリマー材に有酸素雰囲気下で紫外線を照射する工程。
工程Ｃ：工程Ｂで得られたシクロオレフィンポリマー材を水洗する工程。 A surface modification method for a cycloolefin polymer material,
A method for modifying a surface of a cycloolefin polymer material, comprising the following steps A to C.
Process A: The process of degreasing the surface of a cycloolefin polymer material.
Step B: A step of irradiating the cycloolefin polymer material with ultraviolet rays in an aerobic atmosphere.
Step C: A step of washing the cycloolefin polymer material obtained in Step B with water.
以下の工程Ｉ及び工程ＩＩを含むことを特徴とする金属皮膜を形成する方法。
工程Ｉ：表面改質シクロオレフィンポリマー材に金属薄膜層を形成する工程。
工程ＩＩ：前記金属薄膜層の上に電解めっきする工程。 A method for forming a metal film on the surface of the surface-modified cycloolefin polymer material according to claim 4,
A method for forming a metal film comprising the following steps I and II.
Step I: A step of forming a metal thin film layer on the surface-modified cycloolefin polymer material.
Step II: Step of electrolytic plating on the metal thin film layer.
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| JP2011063854A (en) * | 2009-09-17 | 2011-03-31 | Toyota Industries Corp | Method for manufacturing base material to be electroless-plated |
| JPWO2010024175A1 (en) * | 2008-08-25 | 2012-01-26 | 株式会社関東学院大学表面工学研究所 | Laminated body and method for producing the same |
| JP2014011047A (en) * | 2012-06-29 | 2014-01-20 | Canon Components Inc | Shielded cable, manufacturing method of the same, and wireless communication module |
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