JP2001073159A - Formation of electric conductive film on surface of polyimide resin - Google Patents
Formation of electric conductive film on surface of polyimide resinInfo
- Publication number
- JP2001073159A JP2001073159A JP24766799A JP24766799A JP2001073159A JP 2001073159 A JP2001073159 A JP 2001073159A JP 24766799 A JP24766799 A JP 24766799A JP 24766799 A JP24766799 A JP 24766799A JP 2001073159 A JP2001073159 A JP 2001073159A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide resin
- copper
- palladium
- carboxyl group
- solution
- 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
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】ポリイミド樹脂は、分子中で
イミド五員環を介してモノマー単位が連結されているポ
リマー樹脂であり、例えば、オキシジアニリンと無水ピ
ロメリット酸との反応から生成するものが挙げられる。
ポリイミド樹脂は、耐熱性、難燃性、機械的強度及び電
気特性等に優れているため、電子部品や、機械部品等の
広い分野に利用されている。特に、近年のエレクトロニ
クスの急激な進歩に伴って、フレキシブルプリント配線
板（ＦＰＣ）をはじめ、ＴＡＢ用フィルムキャリア、多
層配線板などに広く利用されている。従来、ポリイミド
フィルム上に接着剤を用いないで銅箔を形成する方法に
は、蒸着法や、キャスト法、めっき法等がある。特に、
従来から広く利用されているめっき法としての無電解銅
めっき法は、ＰＴＨには適用されているが、ポリイミド
樹脂上に形成した銅箔に対しては、十分なピール強度を
付与するのが困難である。また、無電解銅めっき液は、
使用されるホルマリンの発癌性の問題や、キレート剤の
排水規制等によって、その使用が問題となっている。BACKGROUND OF THE INVENTION A polyimide resin is a polymer resin in which monomer units are linked via a five-membered imide ring in the molecule. For example, a polyimide resin formed by the reaction between oxydianiline and pyromellitic anhydride Is mentioned.
BACKGROUND ART Polyimide resins are excellent in heat resistance, flame retardancy, mechanical strength, electrical properties, and the like, and are therefore used in a wide range of fields such as electronic components and mechanical components. In particular, with the rapid progress of electronics in recent years, it is widely used for flexible printed wiring boards (FPC), film carriers for TAB, multilayer wiring boards, and the like. Conventionally, methods for forming a copper foil on a polyimide film without using an adhesive include a vapor deposition method, a casting method, a plating method, and the like. In particular,
Electroless copper plating, which has been widely used in the past, has been applied to PTH, but it is difficult to impart sufficient peel strength to copper foil formed on polyimide resin. It is. In addition, the electroless copper plating solution
Due to the carcinogenicity of the used formalin and the regulation of drainage of chelating agents, its use has become a problem.
【０００２】[0002]
【発明が解決しようとする課題】従って、本発明は、接
着剤を使用せずに、直接ポリイミド樹脂表面に、ピール
強度の向上した金属の導電性薄膜又はパターンを形成す
る方法を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for forming a metal conductive thin film or pattern having improved peel strength directly on a polyimide resin surface without using an adhesive. Aim.
【０００３】[0003]
【問題を解決するための手段】本発明者らは、上記課題
を達成するため、鋭意検討した結果、以下の方法によっ
て、上記課題が確実に達成できることを見出し、本発明
に到達したものである。即ち、本発明は、以下の発明に
ある。 １．ポリイミド樹脂表面に銅又はパラジウムからなる導
電性皮膜を形成する方法であって、以下の工程： （１）ポリイミド樹脂表面をアルカリ水溶液で処理し
て、前記ポリイミド樹脂のイミド環を開環してカルボキ
シル基を生成する工程、（２）前記カルボキシル基を中
和する工程、（３）前記カルボキシル基を、銅又はパラ
ジウム溶液で処理することにより、前記カルボキシル基
の銅又はパラジウム塩を生成する工程、及び（４）前記
銅又はパラジウム塩を還元して、前記ポリイミド樹脂表
面に前記銅又はパラジウム金属の皮膜を形成する工程、
を含有することを特徴とする方法。 ２．ポリイミド樹脂表面に銅又はパラジウムからなる導
電性皮膜パターンを形成する方法であって、以下の工
程： （１）ポリイミド樹脂表面をアルカリ水溶液で処理し
て、前記ポリイミド樹脂のイミド環を開環してカルボキ
シル基を生成する工程、（２）前記カルボキシル基を中
和する工程、（３）前記カルボキシル基を、銅又はパラ
ジウム溶液で処理することにより、前記カルボキシル基
の銅又はパラジウム塩を生成する工程、（４）前記銅又
はパラジウム塩を表面に有する前記ポリイミド樹脂の表
面に還元剤を塗布する工程、及び（５）前記ポリイミド
樹脂の表面にマスクパターンを通して紫外線を照射する
工程、を含有することを特徴とする方法。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the above object can be surely achieved by the following method, and have reached the present invention. . That is, the present invention resides in the following inventions. 1. A method for forming a conductive film made of copper or palladium on the surface of a polyimide resin, comprising the following steps: (1) treating the surface of the polyimide resin with an aqueous alkali solution to open the imide ring of the polyimide resin to form a carboxyl group; (2) a step of neutralizing the carboxyl group, (3) a step of treating the carboxyl group with a copper or palladium solution to produce a copper or palladium salt of the carboxyl group, and (4) a step of reducing the copper or palladium salt to form the copper or palladium metal film on the surface of the polyimide resin;
The method characterized by containing. 2. A method for forming a conductive film pattern made of copper or palladium on a polyimide resin surface, comprising the following steps: (1) treating the polyimide resin surface with an aqueous alkali solution to open the imide ring of the polyimide resin; Generating a carboxyl group, (2) neutralizing the carboxyl group, (3) treating the carboxyl group with a copper or palladium solution to generate a copper or palladium salt of the carboxyl group, (4) a step of applying a reducing agent to the surface of the polyimide resin having the copper or palladium salt on the surface, and (5) a step of irradiating the surface of the polyimide resin with ultraviolet rays through a mask pattern. And how.
【０００４】[0004]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明で使用されるポリイミド樹脂としては、分
子中でイミド五員環を介してモノマー単位が連結されて
いるポリマーであれば、特に制限なく、各種のポリイミ
ド樹脂を使用することができる。このようなポリイミド
樹脂としては、例えば東レ・デュポン社製カプトンフィ
ルム１００−Ｈや、２００−Ｈ等が使用できる。まず、
ポリイミド樹脂は、アルカリ水溶液によって処理する。
この処理には、例えば、このアルカリ水溶液中にポリイ
ミド樹脂を浸漬することによって容易に行うことが可能
である。アルカリ水溶液としては、水酸化カリウムや水
酸化ナトリウムの水溶液を使用することができる。この
アルカリ水溶液処理により、例えば、図１に示されるよ
うに、ポリイミド樹脂のイミド環が開環して、ポリアミ
ド酸を生成する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyimide resin used in the present invention is not particularly limited as long as it is a polymer in which monomer units are linked via a five-membered imide ring in the molecule, and various polyimide resins can be used. As such a polyimide resin, for example, Kapton film 100-H or 200-H manufactured by Du Pont-Toray Co., Ltd. can be used. First,
The polyimide resin is treated with an aqueous alkali solution.
This treatment can be easily performed, for example, by immersing the polyimide resin in the alkaline aqueous solution. As the alkaline aqueous solution, an aqueous solution of potassium hydroxide or sodium hydroxide can be used. By this alkali aqueous solution treatment, for example, as shown in FIG. 1, the imide ring of the polyimide resin is opened to generate polyamic acid.
【０００５】アルカリ水溶液の濃度は、一般に、３〜１
０Ｍ、好ましくは、４〜６Ｍである。１０Ｍ以上では、
ポリイミド樹脂への反応が激しくなり過ぎ、素地の劣化
を引き起こし易い。処理温度は、一般に、２０〜７０
℃、好ましくは、５０〜６０℃である。処理時間は、通
常、３〜１０分でよく、好ましくは、４〜６分である。
アルカリ水溶液で処理されたポリイミド樹脂は、次い
で、中和される。中和は、カルボキシル基への変換によ
り強アルカリ性に変化した樹脂表面を、酸性溶液によっ
て中和することを目的としている。酸としては、例え
ば、塩酸等を使用できる。酸の濃度は、例えば、０．５
〜１０Ｍ、好ましくは、４〜６Ｍである。処理温度は、
例えば、１５〜５０℃、好ましくは、２０〜３０℃であ
る。処理時間は、通常、０．５〜５分、好ましくは、１
〜２分である。[0005] The concentration of the alkaline aqueous solution is generally 3 to 1
0M, preferably 4-6M. At 10M or more,
The reaction to the polyimide resin becomes too violent, and the base is likely to deteriorate. The processing temperature is generally between 20 and 70
° C, preferably 50 to 60 ° C. The processing time may be usually from 3 to 10 minutes, preferably from 4 to 6 minutes.
The polyimide resin treated with the alkaline aqueous solution is then neutralized. The purpose of the neutralization is to neutralize the resin surface, which has been converted to a strong alkali by conversion into a carboxyl group, with an acidic solution. As the acid, for example, hydrochloric acid or the like can be used. The concentration of the acid is, for example, 0.5
10 to 10M, preferably 4 to 6M. The processing temperature is
For example, it is 15 to 50 ° C, preferably 20 to 30 ° C. The processing time is usually 0.5 to 5 minutes, preferably 1 to 5 minutes.
~ 2 minutes.
【０００６】このように中和したポリイミド樹脂は、そ
のカルボキシル基を導電性皮膜用の金属イオンの塩とす
るために、銅又はパラジウム溶液で処理する。銅又はパ
ラジウム溶液中の銅又はパラジウムイオンの濃度は、例
えば、０．０１〜１Ｍ、好ましくは、０．０４〜０．
０．１Ｍである。必要ならば、銅又はパラジウム溶液中
にエチレンジアミン等のキレート剤や緩衝剤を配合して
もよい。処理温度は、一般に、１０〜４０℃、好ましく
は、２０〜３０℃である。処理時間は、１〜１０分、好
ましくは、３〜７分である。The thus neutralized polyimide resin is treated with a copper or palladium solution in order to convert the carboxyl group into a metal ion salt for a conductive film. The concentration of the copper or palladium ion in the copper or palladium solution is, for example, 0.01 to 1 M, preferably 0.04 to 0.
0.1M. If necessary, a chelating agent such as ethylenediamine or a buffer may be blended in the copper or palladium solution. The processing temperature is generally from 10 to 40C, preferably from 20 to 30C. The processing time is 1 to 10 minutes, preferably 3 to 7 minutes.
【０００７】このようにして形成されたカルボキシル基
の銅又はパラジウム塩を有するポリイミド樹脂は、還元
して、表面に銅又はパラジウム皮膜を有するポリイミド
樹脂を生成する。還元は、例えば、金属塩を表面に有す
るポリイミド樹脂を還元剤と接触することによって行う
ことができる。還元剤としては、例えば、水素化ホウ素
ナトリウムや、次亜リン酸及びその塩、ジメチルアミン
ボラン等を使用することができる。還元剤の濃度は、例
えば、０．００３〜０．０２Ｍ、好ましくは、０．００
５〜０．００７Ｍである。この濃度が、０．００３Ｍ未
満では、還元反応が遅すぎ、一方、その濃度が、０．０
２Ｍを超えると、析出した金属が脱落し易いので好まし
くない。The thus formed polyimide resin having a copper or palladium salt of a carboxyl group is reduced to produce a polyimide resin having a copper or palladium film on the surface. The reduction can be performed, for example, by contacting a polyimide resin having a metal salt on its surface with a reducing agent. As the reducing agent, for example, sodium borohydride, hypophosphorous acid and a salt thereof, dimethylamine borane and the like can be used. The concentration of the reducing agent is, for example, 0.003 to 0.02 M, and preferably 0.003 to 0.02 M.
5 to 0.007M. If this concentration is less than 0.003M, the reduction reaction is too slow, while the concentration is less than 0.03M.
If it exceeds 2M, the deposited metal is likely to fall off, which is not preferable.
【０００８】上記のように、還元剤により処理すること
によって、ポリイミド樹脂の表面に金属皮膜（触媒核）
を形成することができる。一方、例えば、蟻酸水溶液等
の還元剤の溶液を、カルボキシル基の銅又はパラジウム
塩を表面に有するポリイミド樹脂の表面に塗布し、次い
で、例えば、石英ガラスマスクパターンを通して低圧水
銀ランプ電源より紫外線を照射することにより、パター
ン状で金属皮膜（触媒核）を形成することができる。な
お、パターン部以外の部分については、例えば、１％硝
酸水溶液等に浸漬することによって除去できる。As described above, by treating with a reducing agent, a metal film (catalyst nucleus) is formed on the surface of the polyimide resin.
Can be formed. On the other hand, for example, a solution of a reducing agent such as an aqueous solution of formic acid is applied to the surface of a polyimide resin having a copper or palladium salt of a carboxyl group on the surface, and then, for example, ultraviolet rays are irradiated from a low-pressure mercury lamp power supply through a quartz glass mask pattern. By doing so, a metal film (catalyst nucleus) can be formed in a pattern. Note that portions other than the pattern portion can be removed, for example, by immersion in a 1% nitric acid aqueous solution or the like.
【０００９】このようにして形成された銅又はパラジウ
ムからなる導電性金属皮膜又はパターンは、次いで、無
電界銅めっきや、電気銅めっき等の処理を施すことがで
きる。無電界銅めっき処理としては、従来から使用され
ている無電界銅めっき処理を任意に使用することができ
る。このような無電界銅めっき処理としては、例えば、
中性無電界銅めっき処理等が挙げられる。電気銅めっき
処理としては、例えば、硫酸銅めっき処理等が挙げられ
る。中性無電界銅めっき処理に使用される浴組成は、例
えば、以下の通りである。 ＣｕＣｌ2 ０．０５モル／Ｌ Ｃｏ（ＮＯ3）2 ０．１５モル／Ｌ エチレンジアミン ０．６モル／Ｌ アスコルビン酸 ０．０１モル／Ｌ 2,2'−ビピリジル ２０ppm ｐＨ ６．７５ 浴温度 ５０℃ めっき皮膜の厚みとしては、好ましくは、２５〜３０μ
mであることが適当である。[0009] The conductive metal film or pattern made of copper or palladium thus formed can then be subjected to a treatment such as electroless copper plating or electrolytic copper plating. As the electroless copper plating, any conventionally used electroless copper plating can be used. As such an electroless copper plating process, for example,
Neutral electroless copper plating and the like. Examples of the electrolytic copper plating include copper sulfate plating. The bath composition used for the neutral electroless copper plating treatment is, for example, as follows. CuCl 2 0.05 mol / L Co (NO 3 ) 2 0.15 mol / L Ethylenediamine 0.6 mol / L Ascorbic acid 0.01 mol / L 2,2′-bipyridyl 20 ppm pH 6.75 Bath temperature 50 ° C. The thickness of the plating film is preferably 25 to 30 μm.
Suitably, m.
【００１０】硫酸銅めっき処理に使用される浴組成は、
例えば、以下の通りである。 硫酸銅 ７５ｇ／ｌ 硫酸 １９０ｇ／ｌ 塩素 ５０ｐｐｍ ST-901AM（日本リーロナール社製）（光沢剤） ２ｍｌ／ｌ ST-901BM（日本リーロナール社製）（界面活性剤）５ｍｌ／ｌThe bath composition used for the copper sulfate plating treatment is as follows:
For example, it is as follows. Copper sulfate 75 g / l Sulfuric acid 190 g / l Chlorine 50 ppm ST-901AM (manufactured by Nippon Rironal) (brightener) 2 ml / l ST-901BM (manufactured by Nippon Rironal) (surfactant) 5 ml / l
【００１１】めっき皮膜の厚みとしては、好ましくは、
２５〜３０μｍであることが適当である。このようなに
して得られた銅めっき皮膜は、水洗され、汎用の防錆剤
（例えば、メルテックス社製エンテックＣｕ−５６）で
処理した後、更に、水洗され、そして、乾燥され、銅又
はパラジウムからなる導電性皮膜を有するポリイミド樹
脂が得られる。[0011] The thickness of the plating film is preferably
Suitably it is between 25 and 30 μm. The copper plating film thus obtained is washed with water, treated with a general-purpose rust preventive (for example, Entec Cu-56 manufactured by Meltex Co., Ltd.), and further washed with water and dried to obtain copper or copper. A polyimide resin having a conductive film made of palladium is obtained.
【００１２】典型的な導電性皮膜又はパターン形成処理
については、以下の例が挙げられる。A typical example of a conductive film or pattern forming process is as follows.
【００１３】 （例１） カルボキシル基への変換 例えば、５Ｍ ＫＯＨ溶液 水洗 中和 例えば、６Ｍ ＨＣｌ溶液 水洗 金属イオンの吸着 例えばパラジウム塩及び／又は銅塩の水溶液 水洗 還元 例えば、石英ガラスマスクパターンを通して低圧 水銀ランプ 紫外線照射 水洗 無電解銅めっき 無電解銅めっき 水洗 防錆 例えば、メルテックス社製エンテックＣｕ−56 水洗 乾燥Example 1 Conversion to carboxyl group eg 5M KOH solution washing neutralization eg 6M HCl solution washing metal ion adsorption eg aqueous solution of palladium and / or copper salts washing reduction eg low pressure through quartz glass mask pattern Mercury lamp UV irradiation Water washing Electroless copper plating Electroless copper plating Water washing Rust prevention For example, Entec Cu-56 made by Meltex Co., Ltd.
【００１４】 （例２） カルボキシル基の生成 例えば、５Ｍ ＫＯＨ溶液 水洗 中和 例えば、６Ｍ ＨＣｌ溶液 水洗 金属イオンの吸着 例えば、パラジウム塩及び／又は銅塩の水溶液 水洗 還元 例えば、水素化ホウ素ナトリウム溶液 水洗 電気銅めっき 硫酸銅めっき 水洗 防錆 例えば、メルテックス社製エンテックＣｕ−56 水洗 乾燥(Example 2) Formation of carboxyl group, for example, 5M KOH solution, washing neutralization, for example, 6M HCl solution, washing, adsorption of metal ions, eg, aqueous solution of palladium salt and / or copper salt, washing, reduction, eg, sodium borohydride solution, washing Electro-copper plating Copper sulfate plating Rinsing Rust prevention For example, Entec Cu-56 manufactured by Meltex Co.
【００１５】[0015]
【実施例】以下、本発明について、実施例及び比較例に
より更に詳細に説明する。実施例１ ポリイミド樹脂として、東レ・デュポン社製カプトンフ
ィルム２００−Ｈを、５ＭＫＯＨ溶液に５０℃にて５分
浸漬し、イミド環を開環してカルボキシル基をポリイミ
ド樹脂表面上に形成した。このポリイミド樹脂を６Ｍ塩
酸溶液に２５℃で１分浸漬し、中和した。このポリイミ
ド樹脂上における化学変化は、Ｘ線光電子分光分析（Ｘ
ＰＳ）による表面状態分析によって確認した。図２は、
ポリイミド樹脂表面のＸＰＳ（Ｃ１ｓ）スペルトルの変
化を示す。未処理の場合（上図）に比べて、ＫＯＨ＋Ｈ
Ｃｌ処理したものでは、Ｃ１ｓスペクトルのピーク分離
に関して、約２８８．５ｅＶのピークがブロードにな
り、イミド環（Ｏ＝Ｃ−Ｎ−Ｃ＝Ｏ）が開裂し、アミド
結合（Ｏ＝Ｃ−ＮＨ）２８６．９ｅＶとカルボン酸（Ｏ
＝Ｃ−ＯＨ）２８９ｅＶが生成することが分かる。ま
た、２８５〜２８７ｅＶのショルダーの減少は、イミド
結合に隣接するＣ（Ｃ*−ＣＯＮ）の減少を示唆してい
る。以上の結果より、ポリイミド樹脂を５ＭＫＯＨで処
理することにより、イミド環が開裂し、アミド結合とカ
ルボキシル基が生成することか明らかとなった。The present invention will be described below in more detail with reference to examples and comparative examples. Example 1 As a polyimide resin, a Kapton film 200-H manufactured by Du Pont-Toray Co., Ltd. was immersed in a 5M KOH solution at 50 ° C. for 5 minutes to open an imide ring to form a carboxyl group on the surface of the polyimide resin. This polyimide resin was immersed in a 6 M hydrochloric acid solution at 25 ° C. for 1 minute to neutralize it. The chemical change on the polyimide resin is determined by X-ray photoelectron spectroscopy (X
(PS) by surface state analysis. FIG.
3 shows the change in XPS (C1s) spectrum on the polyimide resin surface. Compared to the untreated case (upper figure), KOH + H
In the case of Cl treatment, the peak at about 288.5 eV becomes broad with respect to the peak separation of the C1s spectrum, the imide ring (O = C—N—C = O) is cleaved, and the amide bond (O = C—NH) 286.9 eV and carboxylic acid (O
= C-OH) 289 eV is generated. Also, a decrease in the shoulder of 285-287 eV indicates a decrease in C (C * -CON) adjacent to the imide bond. From the above results, it was clarified that the imide ring was cleaved and the amide bond and the carboxyl group were formed by treating the polyimide resin with 5M KOH.
【００１６】次いで、得られた中和ポリイミド樹脂を、
ＣｕＳＯ4／ＰｄＣｌ2溶液（Ｃｕ2+＋Ｐｄ2+＝０．０５
Ｍ）に０．４Ｍエチレンジアミンを加えた混合溶液に室
温で１分浸漬し、カルボキシル基にＣｕ2+及びＰｄ2+の
塩を形成した（ポリイミド樹脂にこれらの金属イオンを
吸着した）。図３は、ポリイミド樹脂上の吸着したＣｕ
2+及びＰｄ2+の量に対するＰｄＣｌ 2濃度の効果を説明
する。ＰｄＣｌ2濃度の増大に従って、吸着Ｃｕ2+の量
は減少し、吸着Ｐｄ2+量は増大して、ＰｄＣｌ2濃度
０．００５Ｍでは９８０ｎｍｏｌ／ｃｍ2のＣｕ2+、１
０９ｎｍｏｌ／ｃｍ2のＰｄ2+が吸着されたことが分か
る。Next, the obtained neutralized polyimide resin is
CuSOFour/ PdClTwoSolution (Cu2++ Pd2+= 0.05
M) to a mixed solution obtained by adding 0.4 M ethylenediamine
Immersion at room temperature for 1 minute2+And Pd2+of
A salt was formed (these metal ions were added to the polyimide resin
Adsorbed). FIG. 3 shows the adsorption of Cu on the polyimide resin.
2+And Pd2+PdCl to the amount of TwoExplain the effect of concentration
I do. PdClTwoAs the concentration increases, the adsorbed Cu2+Amount of
Decreases and the adsorbed Pd2+The amount is increased to PdClTwoconcentration
980 nmol / cm at 0.005MTwoCu2+, 1
09 nmol / cmTwoPd2+Can be seen that
You.
【００１７】このようにして得られたＣｕ2+及びＰｄ2+
を吸着したカルボキシル基を有するポリイミド樹脂に、
５ＭＨＣＯＯＮａ水溶液(pH６)を塗布し、石英ガラスマ
スターパターンを通して140Wの低圧水銀ランプ電源(特
殊光源株式会社製)より紫外線を1時間照射することによ
り、回路パターンで銅又はパラジウム金属を析出させ
た。回路パターン以外の部分については、1％HNO3水溶
液に樹脂を浸漬することによって金属イオンを除去し
た。次いで、得られた銅又はパラジウム金属からなる導
電性金属層を触媒核として利用して、以下の浴組成を有
する中性無電界銅めっき浴中にポリイミド樹脂を１５分
間浸漬して、回路パターンに対応した銅回路を形成し
た。 ＣｕＣｌ2 ０．０５モル／Ｌ Ｃｏ（ＮＯ3）2 ０．１５モル／Ｌ エチレンジアミン ０．６モル／Ｌ アスコルビン酸 ０．０１モル／Ｌ 2,2'−ビピリジル ２０ppm ｐＨ ６．７５ 浴温度 ５０℃The thus obtained Cu 2+ and Pd 2+
To a polyimide resin having a carboxyl group adsorbing
A 5 MHCOONa aqueous solution (pH 6) was applied, and ultraviolet light was irradiated for 1 hour from a 140 W low-pressure mercury lamp power supply (manufactured by Tokushu Light Source Co., Ltd.) through a quartz glass master pattern to deposit copper or palladium metal in a circuit pattern. For the portions other than the circuit pattern, metal ions were removed by immersing the resin in a 1% HNO 3 aqueous solution. Next, using the obtained conductive metal layer made of copper or palladium metal as a catalyst core, the polyimide resin was immersed in a neutral electroless copper plating bath having the following bath composition for 15 minutes to form a circuit pattern. A corresponding copper circuit was formed. CuCl 2 0.05 mol / L Co (NO 3 ) 2 0.15 mol / L Ethylenediamine 0.6 mol / L Ascorbic acid 0.01 mol / L 2,2′-bipyridyl 20 ppm pH 6.75 Bath temperature 50 ° C.
【００１８】表面状態は、透過型電子顕微鏡（ＳＥＭ）
により観察した。また、表面電気伝導率は、マルチメー
タによって測定した。図４は、このようにして形成され
たポリイミド樹脂表面上における銅パターンの表面モル
ホロジーを示す。ＣｕＳＯ4／ＰｄＣｌ2溶液におけるＰ
ｄＣｌ2濃度の増大に伴い、鮮明な回路が形成される。
ＰｄＣｌ2濃度０．００５Ｍにおいて微細な線及び点に
も析出し、表面電気伝導率は、０．００６９Ｓ／□を示
した。The surface condition is determined by a transmission electron microscope (SEM).
Was observed. The surface electric conductivity was measured with a multimeter. FIG. 4 shows the surface morphology of the copper pattern on the surface of the polyimide resin thus formed. P in CuSO 4 / PdCl 2 solution
As the dCl 2 concentration increases, a clear circuit is formed.
At a PdCl 2 concentration of 0.005M, it was also deposited on fine lines and points, and the surface electrical conductivity was 0.0069 S / □.
【００１９】実施例２ 実施例１に従って、東レ・デュポン社製カプトンフィル
ム２００−Ｈを、５ＭＫＯＨ溶液に５０℃にて５分浸漬
し、イミド環を開環してカルボキシル基をポリイミド樹
脂表面上に形成した。このポリイミド樹脂を６Ｍ塩酸溶
液に２５℃で１分浸漬し、中和した。次いで、得られた
中和ポリイミド樹脂を、０．０５Ｍ塩化パラジウム溶液
に室温にて１分間浸漬して、パラジウムイオンをポリイ
ミド樹脂表面上のカルボキシル基と反応させて、吸着さ
せた後、パラジウム金属塩を有するポリイミド樹脂を
０．００７ＭＮａＢＨ4水溶液に浸漬した。還元処理し
た後の表面は金属光沢を呈していた。このようにして得
られたパラジウム金属からなる導電性金属皮膜を有する
ポリイミド樹脂に対して、硫酸銅めっきを２Ａ／ｄｍ2
にて６０分行い、約２５μｍの銅めっき層を形成した。
この試料を水洗し、乾燥した後、めっき層を１ｍｍ角に
ナイフでカットし、テープ剥離テストを行なった結果、
テープ側への皮膜の付着は認められず良好な密着性を有
していた。 Example 2 In accordance with Example 1, Kapton film 200-H manufactured by Du Pont-Toray Co., Ltd. was immersed in a 5M KOH solution at 50 ° C. for 5 minutes to open the imide ring to form a carboxyl group on the polyimide resin surface. Formed. This polyimide resin was immersed in a 6 M hydrochloric acid solution at 25 ° C. for 1 minute to neutralize it. Next, the obtained neutralized polyimide resin is immersed in a 0.05 M palladium chloride solution at room temperature for 1 minute to allow palladium ions to react with carboxyl groups on the polyimide resin surface and to be adsorbed. Was immersed in a 0.007 M NaBH 4 aqueous solution. The surface after the reduction treatment had a metallic luster. The polyimide resin having a conductive metal film made of palladium metal thus obtained was subjected to copper sulfate plating at 2 A / dm 2.
For 60 minutes to form a copper plating layer of about 25 μm.
After the sample was washed with water and dried, the plating layer was cut into a 1 mm square with a knife, and a tape peeling test was performed.
Adhesion of the film on the tape side was not observed, and the tape had good adhesion.
【００２０】実施例３ 東レ・デュポン社製カプトンフィルム２００−Ｈを、５
ＭＫＯＨ溶液に５０℃で５分浸漬し、イミド環を開環し
て表面にカルボキシル基を生成したポリイミド樹脂を、
６Ｍ塩酸溶液に２５℃で１分浸漬して、中和した後、
０．０２５Ｍ硫酸銅、０．０２５Ｍ塩化パラジウム混合
水溶液に室温で１分間浸漬して、銅及びパラジウム塩と
してのカルボキシル基を有するポリイミド樹脂を生成し
た後、５Ｍ蟻酸水溶液を塗布した。次に、石英ガラスマ
スクパターンを通して１４０Ｗの低圧水銀ランプ電源よ
り紫外線を１時間照射した。回路パターン以外に残存す
る金属イオンを１％硝酸溶液にて溶離除去した。触媒核
が形成されたポリイミド樹脂は、実施例１で使用したも
のと同様の中性無電解銅めっき液に１５分浸漬し、銅回
路を形成した。この試料を水洗し、乾燥した後、ポリイ
ミド樹脂上の金属皮膜を１ｍｍ角にナイフでカットし、
テープ剥離テストを行なった結果、テープ側への皮膜の
付着は認められず、良好な密着性を有していた。 Example 3 A Kapton film 200-H manufactured by Dupont Toray Co., Ltd.
A polyimide resin which was immersed in an MKOH solution at 50 ° C. for 5 minutes to form a carboxyl group on the surface by opening the imide ring,
After immersion in a 6 M hydrochloric acid solution at 25 ° C. for 1 minute for neutralization,
A polyimide resin having a carboxyl group as a copper and palladium salt was generated by immersing in a mixed aqueous solution of 0.025 M copper sulfate and 0.025 M palladium chloride for 1 minute at room temperature, and then a 5 M aqueous solution of formic acid was applied. Next, ultraviolet light was irradiated for 1 hour from a 140 W low-pressure mercury lamp power supply through a quartz glass mask pattern. The remaining metal ions other than the circuit pattern were eluted and removed with a 1% nitric acid solution. The polyimide resin on which the catalyst nuclei were formed was immersed in the same neutral electroless copper plating solution as used in Example 1 for 15 minutes to form a copper circuit. After this sample was washed with water and dried, the metal film on the polyimide resin was cut into a 1 mm square with a knife,
As a result of a tape peeling test, no film was adhered to the tape side, and the tape had good adhesion.
【００２１】実施例４ 東レ・デュポン社製カプトンフィルム２００−Ｈを、５
ＭＮａＯＨ溶液に５０℃で５分浸漬し、イミド環を開環
して表面にカルボキシル基を有するポリイミド樹脂を、
６Ｍ塩酸溶液に２５℃で１分浸漬した後、０．０５ＭＰ
ｄＣｌ2溶液に室温で１分間浸漬して、パラジウムイオ
ンをカルボキシル基に吸着させた。次に、得られたポリ
イミド樹脂を０．００７ＭＮａＢＨ4水溶液で還元し
て、パラジウムからなる導電性金属皮膜を形成した。還
元処理後の表面は金属光沢を呈していた。この試料を水
洗し、乾燥した後、金属皮膜を１ｍｍ角にナイフでカッ
トし、テープ剥離テストを行なった結果、テープ側への
皮膜の付着は認められず、良好な密着性を有していた。 Example 4 A Kapton film 200-H manufactured by Dupont Toray Co., Ltd.
A polyimide resin having a carboxyl group on the surface by immersing in an MNaOH solution at 50 ° C. for 5 minutes to open the imide ring,
After immersion in a 6M hydrochloric acid solution at 25 ° C for 1 minute,
It was immersed in a dCl 2 solution for 1 minute at room temperature to adsorb palladium ions to carboxyl groups. Next, the obtained polyimide resin was reduced with a 0.007 M NaBH 4 aqueous solution to form a conductive metal film made of palladium. The surface after the reduction treatment had a metallic luster. After this sample was washed with water and dried, the metal film was cut into a 1 mm square with a knife, and a tape peeling test was performed. As a result, no film was adhered to the tape side, and the tape had good adhesion. .
【００２２】実施例５ 東レ・デュポン社製カプトンフィルム２００−Ｈを、５
ＭＫＯＨ溶液に５０℃で５分浸漬し、イミド環を開環し
て表面にカルボキシル基を有するポリイミド樹脂を、６
Ｍ塩酸溶液に２５℃で１分浸漬し、中和した後、０．０
５ＭＰｄＣｌ2水溶液に室温で１分間浸漬し、パラジウ
ムイオンを吸着後、５Ｍ蟻酸水溶液を塗布した。その
後，石英ガラスマスクパターンを通して１４０Ｗの低圧
水銀ランプ電源より紫外線を１時間照射した。回路部以
外に残存する金属イオンを１％硝酸溶液にて溶離除去し
た。回路パターンで触媒核が形成されたポリイミド樹脂
は、実施例１で使用した中性無電解銅めっき液に１５分
浸漬し、銅回路を形成した。この試料を水洗し、乾燥し
た後、金属皮膜を１ｍｍ角にナイフでカットし、テープ
剥離テストを行なった結果、テープ側への皮膜の付着は
認められず、良好な密着性を有していた。 Example 5 Kapton film 200-H manufactured by Du Pont-Toray Co., Ltd.
The polyimide resin having a carboxyl group on its surface was immersed in an MKOH solution at 50 ° C. for 5 minutes to open the imide ring,
After immersion in a 25% hydrochloric acid solution at 25 ° C. for 1 minute to neutralize,
After immersion in a 5MPdCl 2 aqueous solution for 1 minute at room temperature to adsorb palladium ions, a 5M aqueous solution of formic acid was applied. Thereafter, ultraviolet light was irradiated for 1 hour from a low-pressure mercury lamp power supply of 140 W through a quartz glass mask pattern. Metal ions remaining outside the circuit were eluted and removed with a 1% nitric acid solution. The polyimide resin having the catalyst nuclei formed in the circuit pattern was immersed in the neutral electroless copper plating solution used in Example 1 for 15 minutes to form a copper circuit. After this sample was washed with water and dried, the metal film was cut into a 1 mm square with a knife, and a tape peeling test was performed. As a result, no film was adhered to the tape side, and the tape had good adhesion. .
【００２３】中性無電解銅めっきの組成及びめっき条件 ＣｕＳＯ4 ０．１５モル／Ｌ トリエタノールアミン ０．７０モル／Ｌ ＨＥＤＴＡ ０．０２モル／Ｌ ＤＭＡＢ ０．０７モル／Ｌ チオシアン酸アンモニウム １ｐｐｍ ＰＥＧ１５４０ １００ｐｐｍ ｐＨ ８．０ 浴温度 ５０℃ Composition and plating conditions of neutral electroless copper plating CuSO 4 0.15 mol / L triethanolamine 0.70 mol / L HEDTA 0.02 mol / L DMAB 0.07 mol / L Ammonium thiocyanate 1 ppm PEG1540 100 ppm pH 8.0 Bath temperature 50 ° C
【００２４】比較例１ １８Ｍ硫酸に６０℃にて４分浸漬しスルホ基を導入した
東レ・デュポン社製カプトンフィルム２００−Ｈを、１
Ｍ水酸化カリウム／エタノール溶液に２５℃で２分浸漬
した後、０．０５Ｍ硫酸銅溶液に室温で５分浸漬し、銅
イオンを吸着した後、０．００７ＭＮａＢＨ4水溶液に
より還元した。還元処理後の表面には金属薄膜が形成さ
れなかった。 Comparative Example 1 Kapton film 200-H manufactured by Dupont Toray Co., Ltd.
After immersion in a 25 M potassium hydroxide / ethanol solution at 25 ° C. for 2 minutes, immersion in a 0.05 M copper sulfate solution at room temperature for 5 minutes to adsorb copper ions, and reduction with a 0.007 M NaBH 4 aqueous solution. No metal thin film was formed on the surface after the reduction treatment.
【００２５】[0025]
【発明の効果】本発明は、接着剤を使用することなく、
ポリイミド樹脂表面上に銅又はパラジウムからなる導電
性皮膜又はそのパターンを形成することができる。According to the present invention, without using an adhesive,
A conductive film made of copper or palladium or a pattern thereof can be formed on the polyimide resin surface.
【図１】アルカリにより、ポリイミド樹脂のイミド環が
どのように開環するのかを例示する。FIG. 1 illustrates how an imide ring of a polyimide resin is opened by an alkali.
【図２】ポリイミド樹脂表面のＸＰＳ（Ｃ１ｓ）スペル
トルの変化を示す。FIG. 2 shows a change in XPS (C1s) spectrum on a polyimide resin surface.
【図３】ポリイミド樹脂上の吸着したＣｕ2+及びＰｄ2+
の量に対するＰｄＣｌ2濃度の効果を説明する。FIG. 3: Cu 2+ and Pd 2+ adsorbed on polyimide resin
The effect of the PdCl 2 concentration on the amount of PdCl 2 will be described.
【図４】ポリイミド樹脂表面上における銅パターンの表
面モルホロジーを示す。FIG. 4 shows the surface morphology of a copper pattern on a polyimide resin surface.
Claims (2)
らなる導電性皮膜を形成する方法であって、以下の工
程： （１）ポリイミド樹脂表面をアルカリ水溶液で処理し
て、前記ポリイミド樹脂のイミド環を開環してカルボキ
シル基を生成する工程、（２）前記カルボキシル基を中
和する工程、（３）前記カルボキシル基を、銅又はパラ
ジウム溶液で処理することにより、前記カルボキシル基
の銅又はパラジウム塩を生成する工程、及び（４）前記
銅又はパラジウム塩を還元して、前記ポリイミド樹脂表
面に前記銅又はパラジウム金属の皮膜を形成する工程、
を含有することを特徴とする方法。1. A method for forming a conductive film made of copper or palladium on a surface of a polyimide resin, comprising the following steps: (1) treating the surface of the polyimide resin with an aqueous alkali solution to form an imide ring of the polyimide resin; (2) neutralizing the carboxyl group, (3) treating the carboxyl group with a copper or palladium solution to convert the copper or palladium salt of the carboxyl group. Generating, and (4) reducing the copper or palladium salt to form the copper or palladium metal film on the polyimide resin surface,
The method characterized by containing.
らなる導電性皮膜パターンを形成する方法であって、以
下の工程：（１）ポリイミド樹脂表面をアルカリ水溶液
で処理して、前記ポリイミド樹脂のイミド環を開環して
カルボキシル基を生成する工程、（２）前記カルボキシ
ル基を中和する工程、（３）前記カルボキシル基を、銅
又はパラジウム溶液で処理することにより、前記カルボ
キシル基の銅又はパラジウム塩を生成する工程、（４）
前記銅又はパラジウム塩を表面に有する前記ポリイミド
樹脂の表面に還元剤を塗布する工程、及び（５）前記ポ
リイミド樹脂の表面にマスクパターンを通して紫外線を
照射する工程、を含有することを特徴とする方法。2. A method for forming a conductive film pattern made of copper or palladium on a surface of a polyimide resin, comprising the steps of: (1) treating the surface of the polyimide resin with an aqueous alkali solution to form an imide ring of the polyimide resin; To form a carboxyl group by ring opening, (2) a step of neutralizing the carboxyl group, and (3) a treatment of the carboxyl group with a copper or palladium solution to form a copper or palladium salt of the carboxyl group. Generating (4)
Applying a reducing agent to the surface of the polyimide resin having the copper or palladium salt on the surface thereof, and (5) irradiating the surface of the polyimide resin with ultraviolet light through a mask pattern. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24766799A JP2001073159A (en) | 1999-09-01 | 1999-09-01 | Formation of electric conductive film on surface of polyimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24766799A JP2001073159A (en) | 1999-09-01 | 1999-09-01 | Formation of electric conductive film on surface of polyimide resin |
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| Publication Number | Publication Date |
|---|---|
| JP2001073159A true JP2001073159A (en) | 2001-03-21 |
Family
ID=17166881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24766799A Pending JP2001073159A (en) | 1999-09-01 | 1999-09-01 | Formation of electric conductive film on surface of polyimide resin |
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| Country | Link |
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1999
- 1999-09-01 JP JP24766799A patent/JP2001073159A/en active Pending
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