JP3409557B2 - Electroless plating method - Google Patents
Electroless plating methodInfo
- Publication number
- JP3409557B2 JP3409557B2 JP01535996A JP1535996A JP3409557B2 JP 3409557 B2 JP3409557 B2 JP 3409557B2 JP 01535996 A JP01535996 A JP 01535996A JP 1535996 A JP1535996 A JP 1535996A JP 3409557 B2 JP3409557 B2 JP 3409557B2
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- plated
- noble metal
- metal compound
- plasma
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、無電解メッキ方法
に関するものであり、特に、無電解メッキに不可欠な、
無電解メッキ用触媒核の活性化処理方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless plating method, and in particular, it is indispensable for electroless plating.
The present invention relates to a method for activating a catalytic nucleus for electroless plating.
【０００２】[0002]
【従来の技術】従来より、無電解メッキは、プラスチッ
ク、ガラス、セラミック等の絶縁物表面を金属化する方
法として用いられている。この無電解メッキの方法とし
ては、各種のエッチング方法により被メッキ物の表面を
粗面化及び親水化させた後、被メッキ物に無電解メッキ
の触媒核を付与（核付け処理）し、次いで、その触媒核
を活性化（活性化処理）した後、無電解メッキ液に浸漬
することにより、無電解メッキ皮膜を析出させる方法
が、一般に行われている。2. Description of the Related Art Conventionally, electroless plating has been used as a method for metallizing the surface of an insulating material such as plastic, glass or ceramic. As the method of this electroless plating, after roughening and hydrophilizing the surface of the object to be plated by various etching methods, a catalytic nucleus of the electroless plating is applied to the object to be plated (nucleation treatment), and then Generally, a method of activating (activating treatment) the catalyst nucleus and then immersing it in an electroless plating solution to deposit an electroless plating film is performed.
【０００３】無電解メッキにおいては、核付け処理及び
活性化処理が重要な工程であり、これらの処理の良し悪
しが無電解メッキ皮膜の析出性、密着性に影響を及ぼ
す。In electroless plating, nucleation treatment and activation treatment are important steps, and the quality of these treatments affects the deposition and adhesion of the electroless plating film.
【０００４】そのため、これらの方法として、塩化スズ
溶液に被メッキ物を浸漬し、表面に２価のスズイオンを
吸着させた後、塩化パラジウム溶液に浸漬することによ
り、パラジウムイオンを還元し、活性なパラジウム触媒
核を表面に付着させるセンシーアクチ法や、被メッキ物
をコンディショナー溶液に浸漬し、表面を触媒核が付着
し易いように調整し、次いでプリディツプ溶液に浸漬し
た後、コロイド状態の触媒核を含有するキャタリスト溶
液に浸漬して、表面に触媒核を付着させ、次いで、アク
セレーターと呼ばれる活性化液に浸漬することにより、
触媒核を活性化するコロイド法等が検討され行われてい
る。Therefore, as these methods, an object to be plated is dipped in a tin chloride solution to adsorb divalent tin ions on the surface, and then dipped in a palladium chloride solution to reduce the palladium ion and activate the active material. Sensitive act method for attaching palladium catalyst nuclei to the surface, or immersing an object to be plated in a conditioner solution to adjust the surface so that the catalyst nuclei can easily adhere, and then immersing it in a pre-dip solution, then containing the catalyst nuclei in colloidal state By immersing in a catalyst solution to attach the catalyst nucleus to the surface, and then immersing in an activating solution called an accelerator,
A colloidal method for activating the catalytic nucleus has been studied and carried out.
【０００５】しかし、これらの方法の場合、触媒核の活
性化時及びその直後の水洗で触媒核が脱落しやすく、被
メッキ物表面と無電解メッキ皮膜の密着力のばらつきが
発生しやすいという問題や、処理工程が多く、また湿式
で行うため、各種処理液の浴管理が必要、洗浄水等の多
量の廃液処理が必要というような種々の問題があった。However, in the case of these methods, the catalyst nuclei are liable to fall off during the activation of the catalyst nuclei and by washing with water immediately after that, so that the adhesion force between the surface of the object to be plated and the electroless plating film tends to vary. In addition, since there are many treatment steps and the treatment is performed in a wet manner, there are various problems that bath management of various treatment liquids is required and a large amount of waste liquid treatment such as cleaning water is required.
【０００６】そこで、触媒核を被メッキ物に付与した
後、乾式法で活性化する方法が検討されている（例え
ば、特開昭６４−５５３８７号）。Therefore, a method of applying a catalyst nucleus to the object to be plated and then activating it by a dry method has been studied (for example, JP-A-64-55387).
【０００７】しかし、特開昭６４−５５３８７号の実施
例に記載されているような、薄層の無電解メッキ皮膜を
形成するために、熱分解性の銀またはパラジウムを被メ
ッキ物上に積層した後、熱又はプラズマを用いて活性化
処理を行う方法の場合、活性化処理を熱処理で行うとき
には、４００〜５００℃の熱処理が必要なため、触媒核
が酸化し、被メッキ物表面と無電解メッキ皮膜の密着力
の低下が懸念される問題や、プラズマを用いると低温で
の処理が可能となるが、減圧プラズマを用いる必要があ
るため、真空ポンプ等の減圧用の大がかりな設備が必要
であり、また量産性が劣るという問題や、得られる無電
解メッキ皮膜は均一な薄層の皮膜とはなるものの、被メ
ッキ物表面と無電解メッキ皮膜の密着性が低いという問
題があった。However, in order to form a thin electroless plating film as described in the embodiment of JP-A-64-55387, a thermally decomposable silver or palladium is laminated on an object to be plated. After that, in the case of the method of performing activation treatment using heat or plasma, when the activation treatment is performed by heat treatment, heat treatment at 400 to 500 ° C. is required, so the catalyst nucleus oxidizes and the surface of the object to be plated is not oxidized. There is a concern that the adhesion strength of the electrolytic plating film may be reduced, and it is possible to perform processing at low temperature using plasma, but it is necessary to use low-pressure plasma, so large-scale equipment for vacuuming such as a vacuum pump is required. In addition, there is a problem that the mass productivity is poor, and the obtained electroless plating film is a uniform thin film, but the adhesion between the surface of the object to be plated and the electroless plating film is low.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記問題点を
改善するために成されたもので、その目的とするところ
は、被メッキ物表面に貴金属化合物を付着した後、プラ
ズマ処理で活性化し、次いで無電解メッキを行う無電解
メッキ方法であって、常圧下で処理ができ、かつ、被メ
ッキ物表面と無電解メッキ皮膜の密着性が高い無電解メ
ッキ方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its purpose is to activate a plasma treatment after depositing a noble metal compound on the surface of an object to be plated. Another object of the present invention is to provide an electroless plating method of performing electroless plating, which can be processed under normal pressure and has high adhesion between the surface of the object to be plated and the electroless plating film.
【０００９】[0009]
【課題を解決するための手段】本発明の請求項１に係る
無電解メッキ方法は、被メッキ物表面に貴金属化合物を
付着した後、プラズマ処理で活性化し、次いで無電解メ
ッキを行う無電解メッキ方法において、貴金属化合物を
付着及び活性化する方法が、被メッキ物表面に貴金属化
合物及び未硬化の熱硬化性樹脂を含有する液体を塗布し
た後、その熱硬化性樹脂を硬化し、次いで、常圧で励起
するガスプラズマを用いて常圧でプラズマ処理を行う方
法であることを特徴とする。The electroless plating method according to claim 1 of the present invention is an electroless plating in which a noble metal compound is deposited on the surface of an object to be plated, activated by plasma treatment, and then electroless plated. In the method, a method of depositing and activating a noble metal compound is to apply a liquid containing a noble metal compound and an uncured thermosetting resin to the surface of an object to be plated, cure the thermosetting resin, and then, The method is characterized in that it is a method of performing plasma treatment at atmospheric pressure using gas plasma excited by pressure.
【００１０】本発明の請求項２に係る無電解メッキ方法
は、請求項１記載の無電解メッキ方法において、貴金属
化合物が、パラジウム又は銀の化合物であることを特徴
とする。The electroless plating method according to claim 2 of the present invention is the electroless plating method according to claim 1, wherein the noble metal compound is a compound of palladium or silver.
【００１１】本発明の請求項３に係る無電解メッキ方法
は、請求項１又は請求項２記載の無電解メッキ方法にお
いて、貴金属化合物が、パラジウム又は銀の有機化合物
であることを特徴とする。An electroless plating method according to a third aspect of the present invention is the electroless plating method according to the first or second aspect, wherein the noble metal compound is an organic compound of palladium or silver.
【００１２】本発明の請求項４に係る無電解メッキ方法
は、請求項１から請求項３のいずれかに記載の無電解メ
ッキ方法において、ガスプラズマが還元性ガスを用いて
励起する還元性ガスプラズマであることを特徴とする。An electroless plating method according to a fourth aspect of the present invention is the electroless plating method according to any one of the first to third aspects, wherein the reducing gas is excited by a gas plasma using a reducing gas. It is characterized by being plasma.
【００１３】本発明の請求項５に係る無電解メッキ方法
は、請求項１から請求項４のいずれかに記載の無電解メ
ッキ方法において、ガスプラズマを用いて常圧でプラズ
マ処理を行う方法が、酸化性ガスを用いて励起する酸化
性ガスプラズマで処理した後、還元性ガスを用いて励起
する還元性ガスプラズマで処理する方法であることを特
徴とする。An electroless plating method according to a fifth aspect of the present invention is the electroless plating method according to any one of the first to fourth aspects, in which gas plasma is used to perform plasma treatment at atmospheric pressure. The method is characterized by a method of treating with an oxidizing gas plasma that is excited by using an oxidizing gas, and then performing a treatment with a reducing gas plasma that is excited by using a reducing gas.
【００１４】本発明によると、貴金属化合物及び未硬化
の熱硬化性樹脂を含有する液体を塗布した後、熱硬化性
樹脂を硬化するため、その硬化により、被メッキ物表面
と貴金属化合物を含有する樹脂が強固に接着する。その
ため貴金属化合物を活性化した後メッキ処理を行うと、
被メッキ物表面と密着性が高いメッキ皮膜が得られる。
また、常圧下でプラズマ処理をするため、貴金属化合物
の揮発が少なくなり、無電解メッキをするための触媒核
を確実に被メッキ物表面に形成することができ、被メッ
キ物表面と密着性が高いメッキ皮膜が得られる。According to the present invention, after the liquid containing the noble metal compound and the uncured thermosetting resin is applied, the thermosetting resin is cured, so that the surface of the object to be plated and the noble metal compound are contained by the curing. The resin adheres firmly. Therefore, if you perform plating after activating the noble metal compound,
A plating film with high adhesion to the surface of the object to be plated can be obtained.
Further, since the plasma treatment is performed under normal pressure, the volatilization of the noble metal compound is reduced, and the catalyst nucleus for electroless plating can be reliably formed on the surface of the object to be plated, and the adhesion to the surface of the object to be plated is ensured. A high plating film can be obtained.
【００１５】[0015]
【発明の実施の形態】本発明に係る無電解メッキ方法
は、図１に示す工程フロー図のように、被メッキ物前処
理、塗布、硬化、プラズマ処理及び無電解メッキ処理の
各工程を有する。BEST MODE FOR CARRYING OUT THE INVENTION The electroless plating method according to the present invention, as shown in the process flow chart shown in FIG. 1, has respective steps of pretreatment of an object to be plated, coating, curing, plasma treatment and electroless plating treatment. .
【００１６】被メッキ物前処理の工程は、被メッキ物表
面の汚れ状態等により必要に応じて行われる工程であ
り、例えば、脱脂処理、湯洗処理、粗面化処理等によ
り、被メッキ物表面の洗浄や、粗面化が行われる。な
お、被メッキ物としてはプラスチック、ガラス、セラミ
ック等の絶縁体が使用でき、特に限定されないが、プラ
スチック等の有機樹脂成形体の場合、本発明の無電解メ
ッキ皮膜の密着性を高める効果が大きく好ましい。The step of pretreatment of the object to be plated is a step which is carried out as necessary depending on the contamination state of the surface of the object to be plated, and for example, the object to be plated is subjected to degreasing treatment, hot water washing treatment, surface roughening treatment and the like. The surface is cleaned and roughened. The material to be plated may be an insulator such as plastic, glass, or ceramic, and is not particularly limited, but in the case of an organic resin molded body such as plastic, the effect of enhancing the adhesion of the electroless plating film of the present invention is large. preferable.
【００１７】塗布の工程は、被メッキ物表面に、貴金属
化合物及び未硬化の熱硬化性樹脂を含有する液体を塗布
する工程であり、この液体は、貴金属化合物及び熱硬化
性樹脂を必須として含有し、必要に応じて硬化剤、硬化
助剤、溶剤等を含有する。The coating step is a step of coating a liquid containing a noble metal compound and an uncured thermosetting resin on the surface of the object to be plated, and this liquid essentially contains the noble metal compound and the thermosetting resin. However, if necessary, it contains a curing agent, a curing aid, a solvent and the like.
【００１８】使用する貴金属化合物としては、銀、パラ
ジウム、白金、金等の貴金属化合物が挙げられる。これ
らはプラズマ処理すると、貴金属化合物が分解して金属
微粒子を生成するものであり、例えば、化合物として
は、ハロゲン化物、炭酸塩、無機酸塩、有機酸塩、有機
錯体、無機錯体等の無機あるいは有機化合物が挙げられ
る。なお、パラジウム又は銀の化合物の場合、プラズマ
処理すると無電解メッキ用触媒核としての活性が高くな
り好ましい。また、有機酸塩、有機錯体等の有機化合物
の場合、プラズマ処理で分解されやすく好ましい。な
お、これらの貴金属化合物は、塗布する液体中に２種類
以上を含有していてもよい。Examples of the noble metal compound used include noble metal compounds such as silver, palladium, platinum and gold. When these are treated with plasma, the noble metal compound is decomposed to produce fine metal particles. For example, as the compound, an inorganic or inorganic compound such as a halide, a carbonate, an inorganic acid salt, an organic acid salt, an organic complex or an inorganic complex can be used. Organic compounds are mentioned. In the case of a compound of palladium or silver, plasma treatment is preferable because the activity as a catalyst nucleus for electroless plating is increased. In addition, organic compounds such as organic acid salts and organic complexes are preferable because they are easily decomposed by plasma treatment. Two or more kinds of these noble metal compounds may be contained in the liquid to be applied.
【００１９】貴金属化合物の量としては、特に制限はな
いが、液体中の貴金属化合物の濃度が、０．１〜５重量
％となるように配合すると好ましい。０．１重量％未満
では、被メッキ物の表面に付着する貴金属化合物の量が
少なくなるため、無電解メッキ皮膜が均一に析出しにく
くなり、５重量％を越えると、貴金属化合物が厚く付着
し破断が触媒核層内で起こる場合があるため、無電解メ
ッキとの十分な密着性が得にくくなる。The amount of the noble metal compound is not particularly limited, but it is preferable to add it so that the concentration of the noble metal compound in the liquid is 0.1 to 5% by weight. If it is less than 0.1% by weight, the amount of the noble metal compound attached to the surface of the object to be plated will be small, and it will be difficult to uniformly deposit the electroless plating film. If it exceeds 5% by weight, the noble metal compound will be attached thickly. Since breakage may occur in the catalyst core layer, it becomes difficult to obtain sufficient adhesion with electroless plating.
【００２０】使用する熱硬化性樹脂としては、特に限定
するものではなく、エポキシ樹脂系、ポリイミド樹脂
系、フェノール樹脂系、ポリフェニレンオキサイド樹脂
系等の熱硬化性樹脂が挙げられる。なお、エポキシ樹脂
系等自己硬化性の低い樹脂は、その樹脂を硬化するため
の硬化剤等も熱硬化性樹脂として配合する。The thermosetting resin used is not particularly limited, and examples thereof include epoxy resin type, polyimide resin type, phenol resin type, polyphenylene oxide resin type and the like. A resin having a low self-hardening property such as an epoxy resin is also blended with a curing agent or the like for hardening the resin as a thermosetting resin.
【００２１】なお、塗布する液体に必要に応じて溶剤を
含有させてもよい。使用できる溶剤は特に限定するもの
ではなく、例えば、ＭＥＫ、ＤＭＦ、アセトニトリル、
アセトン等が挙げられる。If desired, the liquid to be applied may contain a solvent. The solvent that can be used is not particularly limited, and examples include MEK, DMF, acetonitrile,
Acetone etc. are mentioned.
【００２２】液体を塗布する方法としては、特に限定さ
れるものではなく、液体中に被メッキ物を浸漬、あるい
は液体を被メッキ物にスプレーする等の方法により塗布
を行う。被メッキ物を液体に浸漬する方法の場合、ｌ〜
５分程度浸漬すると好ましい。また、塗布後溶剤の乾燥
を必要に応じて実施するが、その条件は、室温〜１５０
℃程度の、表面の溶媒が除去できる温度であればよい。
なお、塗布及び乾燥は複数回繰り返してもよい。The method of applying the liquid is not particularly limited, and the application is performed by a method such as immersing the object to be plated in the liquid or spraying the liquid onto the object to be plated. In the case of the method of immersing the object to be plated in a liquid,
It is preferable to soak for about 5 minutes. Further, after coating, the solvent is dried if necessary, under the conditions of room temperature to 150
It may be at a temperature of about ° C at which the solvent on the surface can be removed.
The coating and drying may be repeated multiple times.
【００２３】硬化の工程は、被メッキ物表面に塗布され
た熱硬化性樹脂を硬化させ、貴金属化合物を含有する樹
脂硬化物層を、被メッキ物表面に形成する工程である。
硬化により、被メッキ物表面と貴金属化合物を含有する
樹脂が強固に接着する。そのため以後の工程で、この樹
脂の表面に露出した貴金属化合物を活性化した後メッキ
処理を行うと、高い密着性が得られる。この理由とし
て、密着性の発現要因であるアンカー効果に加え、樹脂
の硬化により貴金属化合物と樹脂の間の結合が形成され
るためと推定される。硬化の条件は、使用する熱硬化性
樹脂の種類により調整するが、１００〜２５０℃程度で
行う。なお、熱硬化性樹脂の硬化は、後工程のプラズマ
処理で、完全には分解しない程度の硬化度であれば、半
硬化の状態でもよい。このような場合には、無電解メッ
キ等により必要な厚みの導体層を形成した後に完全に硬
化させると、さらに被メッキ物表面と無電解メッキ皮膜
の密着性を高めることができる。The curing step is a step of curing the thermosetting resin applied on the surface of the object to be plated to form a resin cured material layer containing a noble metal compound on the surface of the object to be plated.
Upon curing, the surface of the object to be plated and the resin containing the noble metal compound are firmly bonded. Therefore, in the subsequent steps, high adhesion can be obtained by activating the noble metal compound exposed on the surface of the resin and then performing the plating treatment. It is presumed that the reason for this is that, in addition to the anchor effect, which is a factor that develops the adhesiveness, the bond between the noble metal compound and the resin is formed by curing the resin. The curing conditions are adjusted depending on the type of thermosetting resin used, but are performed at about 100 to 250 ° C. The thermosetting resin may be cured in a semi-cured state as long as the degree of curing is such that the thermosetting resin is not completely decomposed in the plasma treatment in the subsequent step. In such a case, when the conductor layer having a required thickness is formed by electroless plating or the like and then completely cured, the adhesion between the surface of the object to be plated and the electroless plating film can be further enhanced.
【００２４】プラズマ処理の工程は、被メッキ物表面に
塗布された貴金属化合物を、常圧で励起するガスプラズ
マで分解させて活性化し、被メッキ物表面に触媒核とな
る金属微粒子を形成する工程である。In the plasma treatment step, the noble metal compound applied to the surface of the object to be plated is decomposed and activated by gas plasma excited at normal pressure to form fine metal particles which become catalytic nuclei on the surface of the object to be plated. Is.
【００２５】常圧で励起するガスプラズマを用いてプラ
ズマ処理する方法を図面に基づいて説明する。図２は本
発明に使用されるプラズマ処理装置を説明する図であ
る。図２に示すように、プラズマ装置は開放系となって
いる反応槽１を備え、この反応槽１の壁面にはガス導入
口７が設けられている。また、反応槽１内には図示しな
い熱電対が差し込まれており、反応槽１内の雰囲気温度
がモニターできるようになっている。また、反応槽１内
には上部電極２と下部電極３の２つの平板状電極が所定
距離を隔てて対面するようにして平行に設置されてお
り、下部電極３の上面には、固体誘電体６が置かれてい
る。上部電極２及び下部電極３はそれぞれ反応槽１とは
電気的に絶縁されており、上部電極２は交流電源に接続
され、下部電極３は接地されている。なお、固体誘電体
６は、上部電極２の下面と下部電極３の上面の両方に設
けられていても良いし、上部電極２の下面にのみ設けら
れていても良い。この固体誘電体６はアーク放電の発生
を防止しグロー放電を継続して発生させる働きをする。A method of plasma treatment using gas plasma excited at normal pressure will be described with reference to the drawings. FIG. 2 is a diagram illustrating a plasma processing apparatus used in the present invention. As shown in FIG. 2, the plasma apparatus includes a reaction tank 1 which is an open system, and a gas inlet 7 is provided on the wall surface of the reaction tank 1. A thermocouple (not shown) is inserted in the reaction tank 1 so that the ambient temperature in the reaction tank 1 can be monitored. Further, in the reaction tank 1, two plate-like electrodes of an upper electrode 2 and a lower electrode 3 are installed in parallel so as to face each other with a predetermined distance, and a solid dielectric material is provided on the upper surface of the lower electrode 3. 6 is placed. The upper electrode 2 and the lower electrode 3 are electrically insulated from the reaction tank 1, the upper electrode 2 is connected to an AC power source, and the lower electrode 3 is grounded. The solid dielectric 6 may be provided on both the lower surface of the upper electrode 2 and the upper surface of the lower electrode 3, or may be provided only on the lower surface of the upper electrode 2. This solid dielectric 6 functions to prevent the occurrence of arc discharge and to continuously generate glow discharge.
【００２６】上部電極２及び下部電極３の間隔は、固体
誘電体６及び被メッキ物４が挿入できるための必要最小
間隔、具体的には処理時のガス流量等にも依存するが５
ｍｍ以下となるように設置されていることが望ましい。The distance between the upper electrode 2 and the lower electrode 3 depends on the minimum distance required for inserting the solid dielectric 6 and the object 4 to be plated, specifically, the gas flow rate at the time of processing.
It is desirable that the size be set to be less than or equal to mm.
【００２７】被メッキ物４は、上部電極２と下部電極３
の間に配置される。なおこの時、被メッキ物４は、上部
電極２及び下部電極３から共に離した状態に保つことが
好ましい。The object to be plated 4 includes an upper electrode 2 and a lower electrode 3.
Placed between. At this time, it is preferable that the object 4 to be plated is kept away from both the upper electrode 2 and the lower electrode 3.
【００２８】貴金属化合物を常圧で励起するガスプラズ
マで処理する条件としては、キャリアガスとして、ヘリ
ウム、アルゴン等の希ガス又は窒素のうち少なくとも一
つを使用し、反応ガスとして、水素、アンモニア等の還
元性ガス又は酸素、二酸化炭素等の酸化性ガスを使用す
る。なお、キャリアガス及び反応ガスとして空気を単独
で使用することも可能である。この場合は、空気中に含
まれる酸素ガスが反応ガスの役割を果たす。なお、還元
性ガスを反応ガスとして使用すると、メッキ皮膜との密
着性が向上し好ましい。また、酸化性ガスプラズマで処
理した後、還元性ガスプラズマで処理すると、更にメッ
キ皮膜との密着性が向上し好ましい。酸化性ガスプラズ
マで処理を行った後、還元性ガスプラズマで処理を行う
と、酸化性ガスプラズマにより、樹脂硬化物層の一部が
プラズマ酸化を受けてエッチングされ、貴金属成分が表
面に露出する量が多くなるため、メッキ皮膜との密着性
がアップすると考えられる。As the conditions for treating the noble metal compound with the gas plasma excited at normal pressure, at least one of rare gas such as helium and argon or nitrogen is used as the carrier gas, and hydrogen, ammonia and the like are used as the reaction gas. The reducing gas or the oxidizing gas such as oxygen or carbon dioxide is used. It is also possible to use air alone as the carrier gas and the reaction gas. In this case, oxygen gas contained in the air serves as a reaction gas. In addition, it is preferable to use a reducing gas as the reaction gas because the adhesion with the plating film is improved. Further, it is preferable that the treatment with the reducing gas plasma after the treatment with the oxidizing gas plasma further improves the adhesion to the plating film. When treatment with reducing gas plasma is performed after treatment with oxidizing gas plasma, part of the cured resin layer undergoes plasma oxidation due to oxidizing gas plasma and is etched, exposing the noble metal component on the surface. Since the amount is large, it is considered that the adhesion with the plating film is improved.
【００２９】プラズマ処理を行う際には、キャリアガス
ボンベ９内のキャリアガスをガス導入口７より反応槽１
内に導入するとともに、上部電極２及び下部電極３に交
流電力を供給する。この交流電力の供給により、上部電
極２及び下部電極３の間にグロー放電が生じ、プラズマ
が励起される。その後、還元性ガスボンベ１０又は酸化
性ガスボンベ１１内の反応ガスを、ガス導入口７より、
キャリアガスとともに反応槽１内に導入して、被メッキ
物４をプラズマ処理することにより、被メッキ物４表面
の貴金属化合物を分解させて活性化し、被メッキ物４表
面に触媒核となる金属微粒子を形成する。なおこの際、
流量調整により反応ガス及びキャリアガスはそれぞれ所
定流量が反応槽１内に導入されるようになっている。こ
のように、常圧で処理をするため、貴金属化合物の揮発
が少なくなり、無電解メッキをするときの触媒核を確実
に被メッキ物４の表面に形成することができる。When performing the plasma treatment, the carrier gas in the carrier gas cylinder 9 is introduced from the gas inlet 7 into the reaction tank 1.
While being introduced into the inside, AC power is supplied to the upper electrode 2 and the lower electrode 3. By the supply of this AC power, glow discharge is generated between the upper electrode 2 and the lower electrode 3, and plasma is excited. After that, the reaction gas in the reducing gas cylinder 10 or the oxidizing gas cylinder 11 is introduced through the gas inlet 7
By introducing the carrier gas together with the carrier gas into the reaction tank 1 and subjecting the object to be plated 4 to plasma treatment, the noble metal compound on the surface of the object to be plated 4 is decomposed and activated, and fine metal particles serving as catalyst nuclei on the surface of the object to be plated 4 To form. At this time,
The reaction gas and the carrier gas are introduced into the reaction tank 1 at predetermined flow rates by adjusting the flow rates. As described above, since the treatment is performed under normal pressure, the volatilization of the noble metal compound is reduced, and the catalyst nucleus for electroless plating can be surely formed on the surface of the object to be plated 4.
【００３０】プラズマ処理の条件として、例えば、以下
のような条件で行うと好ましい。反応ガスとキャリアガ
スの混合割合としては、キャリアガスに対し反応ガスを
１５容積％以下にする。交流電力としては、周波数５０
Ｈｚ〜１３．６ＭＨｚの電力を印加する。処理時間とし
ては、処理条件にもよるが、０．５分〜５分程度とす
る。反応槽内の圧力は常圧で行う。なお、反応槽１内の
圧力は、本発明の効果を達成できる程度であれば、多少
の減圧状態、あるいは、加圧状態で処理を行ってもよ
い。The plasma treatment is preferably performed under the following conditions, for example. The mixing ratio of the reaction gas and the carrier gas is 15% by volume or less of the reaction gas with respect to the carrier gas. AC power has a frequency of 50
Electric power of Hz to 13.6 MHz is applied. The processing time is about 0.5 minutes to 5 minutes, depending on the processing conditions. The pressure in the reaction tank is atmospheric pressure. In addition, the pressure in the reaction tank 1 may be slightly reduced or pressurized so long as the effect of the present invention can be achieved.
【００３１】なお、一台の設備を使ってプラズマ処理を
行うことに限定するものではなく、酸化性ガスプラズマ
で処理する設備と、還元性ガスプラズマで処理する設備
の２台の設備を使用してもよく、また、被メッキ物を連
続的に処理するために、ベルト等の搬送装置を備える
と、連続処理を行うことも可能である。It should be noted that the plasma treatment is not limited to the use of one equipment, and two equipments, that is, an equipment for treating with an oxidizing gas plasma and an equipment for treating with a reducing gas plasma are used. Alternatively, if a conveyor such as a belt is provided to continuously process the object to be plated, continuous processing can be performed.
【００３２】次いで、無電解メッキ処理工程では、無電
解メッキを行う。無電解メッキの方法としては特に限定
するものではなく各種の方法を用いることができる。な
お、無電解メッキ液としては、銅、ニッケル、銀等の各
種メッキ液が使用できる。被メッキ物の表面に活性化さ
れた触媒核が形成されているため、無電解メッキを行う
と、被メッキ物表面と密着性が高いメッキ皮膜が形成さ
れる。Next, in the electroless plating process, electroless plating is performed. The electroless plating method is not particularly limited, and various methods can be used. As the electroless plating solution, various plating solutions such as copper, nickel and silver can be used. Since the activated catalyst nuclei are formed on the surface of the object to be plated, when electroless plating is performed, a plating film having high adhesion to the surface of the object to be plated is formed.
【００３３】[0033]
（実施例１）両面銅張り積層板（ＦＲ−４タイプ）［松
下電工社製 品番Ｒ１７０５］の銅箔をエッチングし、
表面の銅を除去した基板を用意し、水酸化カリウム溶液
で脱脂処理した。次に、表１に示す貴金属化合物、テト
ラブロモビスフェノールＡ型エポキシ樹脂、ジシアンジ
アミド、硬化促進剤及び溶剤を配合した液体に、脱脂処
理した基板を浸漬し、溶剤成分を乾燥した後、１７０℃
に昇温した乾燥機で９０分処理して樹脂を硬化させた。
なお、液体中の貴金属化合物の濃度は表１に示す濃度で
あり、熱硬化性樹脂（テトラブロモビスフェノールＡ型
エポキシ樹脂、ジシアンジアミド、硬化促進剤）の濃度
は０．５重量％であった。(Example 1) A copper foil of a double-sided copper-clad laminate (FR-4 type) [Matsushita Electric Works, Ltd. product number R1705] was etched,
A substrate from which copper on the surface was removed was prepared and degreased with a potassium hydroxide solution. Next, the degreased substrate is immersed in a liquid containing the noble metal compound shown in Table 1, tetrabromobisphenol A type epoxy resin, dicyandiamide, a curing accelerator and a solvent, and the solvent component is dried.
The resin was cured by treating it for 90 minutes in a dryer heated to the above temperature.
The concentration of the noble metal compound in the liquid was as shown in Table 1, and the concentration of the thermosetting resin (tetrabromobisphenol A type epoxy resin, dicyandiamide, curing accelerator) was 0.5% by weight.
【００３４】次いで、ガスプラズマ装置を用いて、常圧
下で、表１に示す還元性ガスを用いて励起する還元性ガ
スプラズマで処理した後、無電解銅メッキ液［シプレイ
社製品番ＣＭ３８５２］に基板を浸漬し、無電解銅メッ
キ皮膜を約０．３μｍ析出させた。なお、プラズマ処理
の条件は、表１に示す条件で行った。Then, after treating with a reducing gas plasma excited by using a reducing gas shown in Table 1 under a normal pressure using a gas plasma device, an electroless copper plating solution [Chipley Company product number CM3852] was prepared. The substrate was dipped to deposit an electroless copper plating film of about 0.3 μm. The plasma treatment was performed under the conditions shown in Table 1.
【００３５】（実施例２）両面銅張り積層板（ＦＲ−４
タイプ）［松下電工社製 品番Ｒ１７６６］の銅箔をエ
ッチングして表面の銅を除去した基板を用いたこと、及
び、表１に示す貴金属化合物、テトラブロモビスフェノ
ールＡ型エポキシ樹脂、フェノールノボラック型エポキ
シ樹脂、ジシアンジアミド、硬化促進剤及び溶剤を配合
した液体を用いたこと、及び、表１に示す条件でプラズ
マ処理を行ったこと以外は実施例１と同様にしてプラズ
マ処理した後、無電解銅メッキを行った。なお、液体中
の貴金属化合物の濃度は表１に示す濃度であり、熱硬化
性樹脂の濃度は０．５重量％であった。(Example 2) Double-sided copper-clad laminate (FR-4)
(Type) [Matsushita Electric Works Co., Ltd. product number R1766] was used as a substrate obtained by etching the copper foil to remove the copper on the surface, and the noble metal compound, tetrabromobisphenol A type epoxy resin, and phenol novolac type epoxy shown in Table 1. After plasma treatment in the same manner as in Example 1 except that a liquid containing a resin, dicyandiamide, a curing accelerator and a solvent was used, and plasma treatment was performed under the conditions shown in Table 1, electroless copper plating was performed. I went. The concentration of the noble metal compound in the liquid was as shown in Table 1, and the concentration of the thermosetting resin was 0.5% by weight.
【００３６】（実施例３）両面銅張り積層板（ＧＰＹタ
イプ）［松下電工社製 品番Ｒ４７７５］の銅箔をエッ
チングして表面の銅を除去した基板を用いたこと、及
び、表１に示す貴金属化合物、ポリアミノビスマレイミ
ド及び溶剤を配合した液体を用いたこと、及び、２００
℃に昇温した乾燥機で１２０分処理して硬化させたこ
と、及び、表１に示す条件で酸化性ガスプラズマで処理
を行った後、還元性ガスプラズマで処理をしたこと以外
は実施例１と同様にしてプラズマ処理した後、無電解銅
メッキを行った。なお、液体中の貴金属化合物の濃度は
表１に示す濃度であり、熱硬化性樹脂の濃度は０．７重
量％であった。(Example 3) A double-sided copper-clad laminate (GPY type) [Matsushita Electric Works, Ltd., product number R4775] was used, in which a copper foil was etched to remove the copper on the surface, and Table 1 shows. Using a liquid containing a noble metal compound, polyamino bismaleimide and a solvent, and 200
Example except that it was cured by being treated with a drier heated to 120 ° C. for 120 minutes, and that it was treated with oxidizing gas plasma under the conditions shown in Table 1 and then with reducing gas plasma. After plasma treatment in the same manner as in No. 1, electroless copper plating was performed. The concentration of the noble metal compound in the liquid was as shown in Table 1, and the concentration of the thermosetting resin was 0.7% by weight.
【００３７】（実施例４）両面銅張り積層板（ポリフェ
ニレンオキサイドタイプ）［松下電工社製 品番Ｒ４７
２６］の銅箔をエッチングして表面の銅を除去した基板
を用いたこと、及び、表１に示す貴金属化合物、ポリ
（２，６−ジメチル−１，４−フェニレンオキサイ
ド）、架橋性樹脂、架橋助剤、ラジカル反応開始剤及び
溶剤を配合した液体を用いたこと、及び、表１に示す条
件で酸化性ガスプラズマで処理を行った後、還元性ガス
プラズマで処理をしたこと以外は実施例１と同様にして
プラズマ処理した後、無電解銅メッキを行った。なお、
液体中の貴金属化合物の濃度は表１に示す濃度であり、
熱硬化性樹脂の濃度は０．５重量％であった。(Example 4) Double-sided copper-clad laminate (polyphenylene oxide type) [Matsushita Electric Works Co., Part No. R47
[26] A substrate obtained by etching the copper foil to remove the copper on the surface is used, and a noble metal compound shown in Table 1, poly (2,6-dimethyl-1,4-phenylene oxide), a crosslinkable resin, Except that a liquid containing a crosslinking aid, a radical reaction initiator and a solvent was used, and that the treatment was performed with an oxidizing gas plasma under the conditions shown in Table 1 and then with a reducing gas plasma. After plasma treatment as in Example 1, electroless copper plating was performed. In addition,
The concentration of the noble metal compound in the liquid is the concentration shown in Table 1,
The concentration of thermosetting resin was 0.5% by weight.
【００３８】（比較例１）実施例１で用いた表面の銅を
除去した基板を用いて、実施例１と同様に脱脂処理を行
った。次いで、コンディショナー溶液［シプレイ社製
品番クリーナコンディショナー２３１］に基板を所定時
間浸漬後、水洗した。次いで、プレディップ溶液［シプ
レイ社製 品番キャタプリップ４０４］に浸漬後、キャ
タリスト溶液［シプレイ社製 品番キャタボジット４
４，キャタプリップ４０４］に浸漬し、水洗してコロイ
ド状態の触媒核を基板表面に付着させた。次いで、アク
セレーター溶液［シプレイ社製 品番アクセレーター１
９］に基板を浸漬した後、水洗した。次いで、実施例１
と同様に無電解銅メッキ液に浸漬し、基板表面に無電解
銅メッキ皮膜を約０．３μｍ析出させた。Comparative Example 1 A degreasing treatment was carried out in the same manner as in Example 1 using the substrate used in Example 1 from which the copper on the surface was removed. Then, a conditioner solution [made by Shipley
The substrate was immersed in the product number cleaner conditioner 231] for a predetermined time and then washed with water. Then, after soaking in the pre-dip solution [Cypley 404 manufactured by Shipley Co., Ltd.], the catalyst solution [Product number Catabotit 4 manufactured by Shipley]
4, cataprep 404] and washed with water to attach the catalyst nuclei in the colloidal state to the substrate surface. Next, accelerator solution [Product number Accelerator 1 manufactured by Shipley Co., Ltd.
9] and then the substrate was washed with water. Then, Example 1
In the same manner as above, it was immersed in an electroless copper plating solution to deposit an electroless copper plating film on the surface of the substrate in an amount of about 0.3 μm.
【００３９】（比較例２）実施例２で用いた表面の銅を
除去した基板を用いたこと以外は比較例１と同様にし
て、無電解銅メッキを行った。(Comparative Example 2) Electroless copper plating was performed in the same manner as in Comparative Example 1 except that the substrate from which the surface copper was removed used in Example 2 was used.
【００４０】（比較例３）実施例３で用いた表面の銅を
除去した基板を用いたこと以外は比較例１と同様にし
て、無電解銅メッキを行った。(Comparative Example 3) Electroless copper plating was carried out in the same manner as in Comparative Example 1 except that the substrate from which the copper on the surface used in Example 3 was removed was used.
【００４１】（比較例４）実施例４で用いた表面の銅を
除去した基板を用いたこと以外は比較例１と同様にし
て、無電解銅メッキを行った。(Comparative Example 4) Electroless copper plating was performed in the same manner as in Comparative Example 1 except that the substrate from which the copper on the surface used in Example 4 was removed was used.
【００４２】[0042]
【表１】 [Table 1]
【００４３】（評価、結果）実施例１〜実施例４及び比
較例１〜比較例４で得られた基板の、メッキ皮膜の密着
性評価として、ピール強度を測定した。方法としては、
硫酸銅電気メッキにより、メッキ皮膜厚合計が約３５ミ
クロンとなるように厚付けした後、基板を１０ｍｍ×１
００ｍｍに切断し、５０ｍｍ／分の引き剥がし速度で測
定した。結果は、表２に示すように、各実施例は各比較
例と比較してピール強度が高く、被メッキ物表面と無電
解メッキ皮膜の密着性が高いことが確認された。(Evaluation, Results) The peel strength was measured as an evaluation of the adhesion of the plating film on the substrates obtained in Examples 1 to 4 and Comparative Examples 1 to 4. As a method,
After plating with copper sulfate electroplating to a total plating film thickness of approximately 35 microns, the substrate was 10 mm x 1
It was cut to 00 mm and measured at a peeling speed of 50 mm / min. As a result, as shown in Table 2, it was confirmed that each example had higher peel strength than each comparative example, and that the adhesion between the surface of the object to be plated and the electroless plating film was high.
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【発明の効果】本発明に係る無電解メッキ方法は、被メ
ッキ物表面に貴金属化合物及び未硬化の熱硬化性樹脂を
含有する液体を塗布した後、熱硬化性樹脂を硬化し、次
いで常圧で励起するガスプラズマを用いてプラズマ処理
を行うため、本発明の無電解メッキ方法を用いると、常
圧下で処理ができ、かつ、被メッキ物表面と密着性が高
いメッキ皮膜が得られる。According to the electroless plating method of the present invention, a liquid containing a noble metal compound and an uncured thermosetting resin is applied to the surface of an object to be plated, the thermosetting resin is then cured, and then the atmospheric pressure is applied. Since the plasma treatment is performed by using the gas plasma excited by, the electroless plating method of the present invention can provide a plating film which can be treated under normal pressure and has high adhesion to the surface of the object to be plated.
【図１】本発明に係る無電解メッキ方法の一実施の形態
の工程フロー図である。FIG. 1 is a process flow chart of an embodiment of an electroless plating method according to the present invention.
【図２】本発明に係る無電解メッキ方法に使用されるプ
ラズマ処理装置を説明する図である。FIG. 2 is a diagram illustrating a plasma processing apparatus used in the electroless plating method according to the present invention.
１ 反応槽 ２ 上部電極 ３ 下部電極 ４ 被メッキ物 ７ ガス導入口 ９ キャリアガスボンベ １０ 還元性ガスボンベ １１ 酸化性ガスボンベ 1 reaction tank 2 upper electrode 3 Lower electrode 4 Plated object 7 gas inlet 9 Carrier gas cylinder 10 Reducing gas cylinder 11 Oxidizing gas cylinder
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−55387（ＪＰ，Ａ) 特開 平１−54718（ＪＰ，Ａ) 特開 平１−17874（ＪＰ，Ａ) 特開 昭63−64393（ＪＰ，Ａ) 特開 昭62−250180（ＪＰ，Ａ) 特開 昭61−102092（ＪＰ，Ａ) 特開 平４−234437（ＪＰ，Ａ) 特開 平４−136184（ＪＰ，Ａ) 特開 平３−199380（ＪＰ，Ａ) 特開 平９−228059（ＪＰ，Ａ) 特許3336796（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 18/20 C23C 18/30 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-55387 (JP, A) JP-A-1-54718 (JP, A) JP-A-1-17874 (JP, A) JP-A-63- 64393 (JP, A) JP 62-250180 (JP, A) JP 61-102092 (JP, A) JP 4-234437 (JP, A) JP 4-136184 (JP, A) JP-A-3-199380 (JP, A) JP-A-9-228059 (JP, A) Patent 3336796 (JP, B2) (58) Fields investigated (Int.Cl. 7 , DB name) C23C 18/20 C23C 18/30
Claims (5)
た後、プラズマ処理で活性化し、次いで無電解メッキを
行う無電解メッキ方法において、貴金属化合物を付着及
び活性化する方法が、被メッキ物表面に貴金属化合物及
び未硬化の熱硬化性樹脂を含有する液体を塗布した後、
その熱硬化性樹脂を硬化し、次いで、常圧で励起するガ
スプラズマを用いて常圧でプラズマ処理を行う方法であ
ることを特徴とする無電解メッキ方法。1. An electroless plating method in which a noble metal compound is deposited on the surface of an object to be plated, then activated by plasma treatment, and then electroless plating is performed, wherein the method of depositing and activating the noble metal compound is a surface of the object to be plated. After applying a liquid containing a noble metal compound and an uncured thermosetting resin to
An electroless plating method, characterized in that the thermosetting resin is cured, and then plasma treatment is performed at normal pressure using gas plasma excited at normal pressure.
合物であることを特徴とする請求項１記載の無電解メッ
キ方法。2. The electroless plating method according to claim 1, wherein the noble metal compound is a palladium or silver compound.
機化合物であることを特徴とする請求項１又は請求項２
記載の無電解メッキ方法。3. The method according to claim 1, wherein the noble metal compound is an organic compound of palladium or silver.
The described electroless plating method.
する還元性ガスプラズマであることを特徴とする請求項
１から請求項３のいずれかに記載の無電解メッキ方法。4. The electroless plating method according to claim 1, wherein the gas plasma is a reducing gas plasma excited with a reducing gas.
理を行う方法が、酸化性ガスを用いて励起する酸化性ガ
スプラズマで処理した後、還元性ガスを用いて励起する
還元性ガスプラズマで処理する方法であることを特徴と
する請求項１から請求項４のいずれかに記載の無電解メ
ッキ方法。5. A method of performing plasma treatment at atmospheric pressure using a gas plasma is a method of treating with an oxidizing gas plasma excited with an oxidizing gas and then using a reducing gas plasma excited with a reducing gas. 5. The electroless plating method according to claim 1, wherein the electroless plating method is a treatment method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01535996A JP3409557B2 (en) | 1996-01-31 | 1996-01-31 | Electroless plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01535996A JP3409557B2 (en) | 1996-01-31 | 1996-01-31 | Electroless plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09209163A JPH09209163A (en) | 1997-08-12 |
| JP3409557B2 true JP3409557B2 (en) | 2003-05-26 |
Family
ID=11886615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01535996A Expired - Fee Related JP3409557B2 (en) | 1996-01-31 | 1996-01-31 | Electroless plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3409557B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100726234B1 (en) * | 2004-06-29 | 2007-06-08 | 삼성전자주식회사 | Antenna device for slide type mobile phone |
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1996
- 1996-01-31 JP JP01535996A patent/JP3409557B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09209163A (en) | 1997-08-12 |
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