JPH07116870A - Processing method for surface of base material - Google Patents
Processing method for surface of base materialInfo
- Publication number
- JPH07116870A JPH07116870A JP5267590A JP26759093A JPH07116870A JP H07116870 A JPH07116870 A JP H07116870A JP 5267590 A JP5267590 A JP 5267590A JP 26759093 A JP26759093 A JP 26759093A JP H07116870 A JPH07116870 A JP H07116870A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- film
- substrate
- ultraviolet laser
- irradiation
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】この発明は、基材表面を粗化する
工程を含む基材表面の処理方法、あるいは、基材表面を
粗化する工程と粗化された基材表面に膜を形成する工程
を含む基材表面の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a substrate surface including a step of roughening a substrate surface, or a step of roughening a substrate surface and forming a film on the roughened substrate surface. The present invention relates to a method for treating a surface of a base material including a step of performing.
【０００２】[0002]
【従来の技術】従来のプリント配線板の製造方法では、
基材表面を粗化した後、粗化された基材表面に導電膜を
形成している。この従来のプリント配線板の製造方法
を、図２４を参照しながら説明する。まず、図２４の最
上段に示す基材２００の表面全面を湿式粗化した後、洗
浄してから、核付けに続いて無電解めっきを施して無電
解めっき膜２０１を形成し、その後、電気めっきを施し
て電気めっき膜２０２を形成する。ついで、レジスト塗
布によりレジスト層２０３を形成してから、露光と現像
によりレジスト層２０３の不要部分を除去して所定パタ
ーンと反対のパターンのレジストマスク２０４を形成し
た後、エッチング処理により非マスク域の無電解めっき
膜２０１および電気めっき膜２０２を選択的に除去し、
ついで、レジストマスク２０４を除去すれば、無電解め
っき膜と電気めっき膜の２層構成の所定パターンの導電
膜２０５が基材２００の表面に形成されたプリント配線
板２０６が得られる（特開昭６１−６８９２号公報）。2. Description of the Related Art In a conventional printed wiring board manufacturing method,
After roughening the substrate surface, a conductive film is formed on the roughened substrate surface. This conventional method for manufacturing a printed wiring board will be described with reference to FIG. First, after wet-roughening the entire surface of the base material 200 shown in the uppermost stage of FIG. 24, cleaning is performed, and then electroless plating is performed following nucleation to form an electroless plated film 201, and then, electroplating is performed. Electroplating film 202 is formed by plating. Next, after forming a resist layer 203 by applying a resist, an unnecessary portion of the resist layer 203 is removed by exposure and development to form a resist mask 204 having a pattern opposite to a predetermined pattern, and then an unmasked area is removed by an etching process. By selectively removing the electroless plated film 201 and the electroplated film 202,
Then, by removing the resist mask 204, a printed wiring board 206 is obtained in which a conductive film 205 of a predetermined pattern having a two-layer structure of an electroless plating film and an electroplating film is formed on the surface of the base material 200 (Japanese Patent Laid-Open Publication No. Sho. 61-6892).
【０００３】しかしながら、上の場合、絶縁基材２００
の表面粗化は、いわゆる薬液処理による湿式粗化である
ため、下記の問題がある。湿式粗化は、アルカリ等の薬
液処理管理の困難さや残留薬液の洗浄処理および環境上
有害な薬液を含む洗浄液の排水に伴う汚染の問題があ
る。湿式粗化の他にホーニングやブラスト処理による機
械的粗化もあるが、従来の機械的粗化では、粗化面の凹
みが浅いことなどから膜密着力を十分に向上させること
は難しく実用性は低い。However, in the above case, the insulating substrate 200
The surface roughening of (1) is so-called wet roughening by a chemical solution treatment, and therefore has the following problems. Wet roughening has problems that it is difficult to control the treatment of chemicals such as alkalis, and that cleaning treatment of residual chemicals and drainage of cleaning fluids containing environmentally harmful chemicals cause pollution. In addition to wet roughening, there is mechanical roughening by honing or blasting, but it is difficult to improve the film adhesion force sufficiently with conventional mechanical roughening because the recesses on the roughened surface are shallow. Is low.
【０００４】[0004]
【発明が解決しようとする課題】この発明は、上記の事
情に鑑みて、湿式粗化を用いずに膜密着力を十分に向上
させられる粗化が基材表面に施せる方法を提供すること
を第１の課題とし、湿式粗化を用いずに膜密着力の十分
な膜を基材表面に形成することのできる方法を提供する
ことを第２の課題とする。In view of the above-mentioned circumstances, the present invention provides a method for roughening the surface of a substrate which can sufficiently improve the film adhesion without using wet roughening. A second object is to provide a method capable of forming a film having a sufficient film adhesion force on the surface of a base material without using wet roughening.
【０００５】[0005]
【課題を解決するための手段】この発明にかかる基材表
面の処理方法は、上記第１の課題を解決するため、基材
表面に紫外レーザを照射して前記基材表面の粗化を行う
工程を含む構成をとるようにしており、第２の課題を解
決するため、基材表面に紫外レーザを照射して前記基材
表面の粗化を行う工程と粗化された基材表面に膜を形成
する工程を含む構成をとっている。In order to solve the above first problem, the method for treating a surface of a base material according to the present invention irradiates an ultraviolet laser on the surface of the base material to roughen the surface of the base material. In order to solve the second problem, a step of irradiating the surface of the base material with an ultraviolet laser to roughen the surface of the base material and a film on the surface of the roughened base material are adopted. Has a structure including a step of forming.
【０００６】以下、この発明をより詳しく説明する。こ
の発明では、粗化のために照射する紫外レーザとして、
通常、波長１００〜４００ｎｍ程度、レーザエネルギー
０．１〜１．０Ｊ／cm2 程度の紫外レーザが使われる。
紫外レーザの波長が、１００ｎｍ未満の場合は空気中で
のレーザ光の減衰が大きく使用できる光学材料も少なく
という不都合が見られる傾向があり、波長４００ｎｍを
超す場合、基材表面への熱影響が大き過ぎて表面が粗化
よりも溶融し易くなるという不都合がみられる傾向があ
る。紫外レーザのエネルギーが０．１Ｊ／cm2 未満の場
合は粗化効果が弱く実用上十分な凹凸が得られないとい
う不都合が見られる傾向があり、１．０Ｊ／cm2 を超す
場合は粗化と同時に被照射基材の分解蒸発が起こり溝部
が形成され後の膜形成に対して好ましくないという不都
合がみられる傾向がある。The present invention will be described in more detail below. In this invention, as an ultraviolet laser for irradiation for roughening,
Usually, an ultraviolet laser having a wavelength of about 100 to 400 nm and a laser energy of about 0.1 to 1.0 J / cm 2 is used.
If the wavelength of the ultraviolet laser is less than 100 nm, there is a tendency that the attenuation of the laser light in the air is large and there are few optical materials that can be used. If the wavelength exceeds 400 nm, there is a thermal effect on the substrate surface. It tends to be too large and the surface tends to melt rather than roughen, which tends to occur. Tend to energy of the ultraviolet laser is observed disadvantageously 0.1 J / cm in the case of less than 2 is not practically sufficient irregularities weak roughening effect obtained, roughened if more than 1.0 J / cm 2 At the same time, there is a tendency that decomposition and evaporation of the substrate to be irradiated occurs and a groove is formed, which is not preferable for subsequent film formation.
【０００７】この発明の基材表面の処理方法の場合、基
材表面への膜形成方法は、限定される訳ではないが、例
えば、無電解めっきや、電気めっき、ＣＶＤなどによる
金属膜の形成法が挙げられるし、さらに、膜自体も無機
膜や有機膜であってもよい。紫外レーザの照射は、基材
表面の全面でなく、特定域（例えば、後形成または同時
形成で所定パターンの膜を設ける膜形成用域）だけに行
うようにしてもよい。In the case of the substrate surface treatment method of the present invention, the method of forming a film on the substrate surface is not limited, but for example, electroless plating, electroplating, CVD or the like to form a metal film. Method, and the film itself may be an inorganic film or an organic film. The irradiation of the ultraviolet laser may be performed not on the entire surface of the base material but only on a specific region (for example, a film forming region where a film having a predetermined pattern is formed by post-formation or simultaneous formation).
【０００８】湿式粗化は膜形成用域のみを粗化する選択
的粗化にも適さないが、紫外レーザの照射による粗化は
膜形成用域のみを粗化する選択的粗化にも適する。湿式
粗化で選択的粗化を行う場合は、非粗化面だけにマスキ
ングテープを貼り付け薬液に浸漬するのであるが、マス
キングテープは余り細くできないため微細（ファイン）
パターン化が難しい上、テープ剥離後に残る接着剤を除
去するためにフロンなどの有機溶剤を使う必要もあるの
に対し、紫外レーザ照射による粗化は、照射を膜形成用
域に限る程度で済むからである。Wet roughening is not suitable for selective roughening for roughening only the film forming area, but roughening by irradiation with an ultraviolet laser is also suitable for selective roughening for roughening only the film forming area. . When performing selective roughening by wet roughening, a masking tape is applied only on the non-roughened surface and immersed in a chemical solution, but the masking tape cannot be made too thin, so it is fine.
While it is difficult to pattern and it is necessary to use an organic solvent such as CFC to remove the adhesive remaining after peeling the tape, roughening by UV laser irradiation only requires irradiation to the film formation area. Because.
【０００９】基材表面の特定域のみに紫外レーザの照射
を行う場合は、図１の（ａ）にみるように、基材１の前
面に膜形成用域に対応する個所が窓となって開いている
マスクを配しておいて、紫外レーザを全面的に当てる
か、図１の（ｂ）にみるように、ビーム状の紫外レーザ
をマスクの上から走査させるか、あるいは、図１の
（ｃ）にみるように、絶縁基材１の前にガルバノミラー
等のスキャンニング機構を設けてビーム状の紫外レーザ
を走査させるか、さらには、図１の（ｄ）にみるよう
に、基材１の表面にビーム状の紫外レーザを当てた状態
で基材１の方をＸ−Ｙテーブル等で移動させ相対的に紫
外レーザを走査させるなどすればよい。When irradiating an ultraviolet laser only on a specific area of the surface of the base material, as shown in FIG. 1 (a), a portion corresponding to the film forming area on the front surface of the base material 1 becomes a window. An open mask is placed and an ultraviolet laser is applied to the entire surface, or a beam-shaped ultraviolet laser is scanned from above the mask as shown in FIG. As shown in (c), a scanning mechanism such as a galvanometer mirror is provided in front of the insulating base material 1 to scan with a beam-shaped ultraviolet laser, or further, as shown in (d) of FIG. The substrate 1 may be moved with an XY table or the like while the beam-shaped ultraviolet laser is applied to the surface of the material 1, and the ultraviolet laser may be relatively scanned.
【００１０】この発明の場合、加えて、紫外レーザの照
射により、粗化された基材表面を光照射により加熱する
こともある。この光照射は、粗化表面に膜を形成する
前、膜形成中、膜形成後の３つのいずれの場合でもよ
い。光照射する粗化面は、基材表面の全面に施されてい
てもよいし、基材表面の特定域だけに施されていてもよ
い。光照射は、例えば、赤外レーザや可視光ビームなど
の熱作用の強い光を粗化表面に照射することで行える。
光照射を伴う加熱により、粗化面の凸部の先端が溶融な
いし軟化して球状化し先端のみが太くなってアンカー効
果を発揮するようになったり、膜形成後の場合は、基板
材料と膜形成材料との間で混合ないし拡散などが起こり
混合域を形成し密着力を強化したりする。In the case of the present invention, in addition, the roughened substrate surface may be heated by light irradiation by irradiation with an ultraviolet laser. This light irradiation may be performed in any of the three cases, before the film is formed on the roughened surface, during the film formation, and after the film formation. The roughened surface to be irradiated with light may be applied to the entire surface of the base material or may be applied only to a specific area of the surface of the base material. The light irradiation can be performed, for example, by irradiating the roughened surface with light having a strong thermal action such as an infrared laser or a visible light beam.
Due to the heating accompanied by light irradiation, the tips of the projections on the roughened surface are melted or softened and become spherical, and only the tips become thicker to exert the anchor effect. Mixing or diffusion occurs with the forming material to form a mixed area and strengthen the adhesion.
【００１１】この発明の場合、基材表面への紫外レーザ
照射を、反応ガスの導入と同反応ガスへのレーザ照射を
伴うレーザＣＶＤの前記反応ガスへのレーザ照射として
も用い、基材表面に対し粗化と同時にレーザＣＶＤによ
る膜の形成を行うようにしてもよい。つまり、この発明
の場合、粗化工程と膜形成工程が同時に行われることも
あるのである。この場合も、基材表面への紫外レーザの
照射は、基材表面の全面でもよいし、特定域だけでもよ
い。In the case of the present invention, the ultraviolet laser irradiation to the substrate surface is also used as the laser irradiation to the reaction gas in the laser CVD accompanied with the introduction of the reaction gas and the laser irradiation to the reaction gas, and the substrate surface is irradiated. On the other hand, the film may be formed by laser CVD simultaneously with the roughening. That is, in the case of the present invention, the roughening step and the film forming step may be simultaneously performed. Also in this case, the irradiation of the ultraviolet laser on the surface of the base material may be performed on the entire surface of the base material or only in a specific area.
【００１２】上に説明した、この発明の様々な態様にお
いて使われる基材は、特定の基材に限られる訳ではな
く、たとえば、樹脂基材、セラミック基材などの絶縁基
材、金属基材などの導電基材が挙げられる。さらに、下
記のような基材Ａ〜Ｆを用いることも有用である。樹脂
基材Ａは、紫外レーザの照射によっても除去されにくい
粒子が表面部分に分散されている樹脂基材である。この
粒子は、必ずしも樹脂基材全体に含まれている必要はな
く、少なくとも粗化を行う領域（例えば、膜形成用域）
に含まれていればよく、普通、樹脂基材全体１００重量
％のうち粒子は１０〜９０重量％を占める。この紫外レ
ーザの照射によっても除去されにくい粒子としては、具
体的に、無機粉末や非粒子部分の樹脂より硬質の樹脂粉
末が挙げられる。The base material used in the various embodiments of the present invention described above is not limited to a specific base material, and may be, for example, an insulating base material such as a resin base material or a ceramic base material, or a metal base material. Conductive base materials such as Further, it is also useful to use the following base materials A to F. The resin base material A is a resin base material in which particles that are difficult to be removed by irradiation with an ultraviolet laser are dispersed in the surface portion. These particles do not necessarily have to be contained in the entire resin base material, and at least a region for roughening (for example, a film forming region)
In general, the particles account for 10 to 90% by weight of the total 100% by weight of the resin base material. Specific examples of the particles that are difficult to be removed by the irradiation of the ultraviolet laser include inorganic powder and resin powder harder than the resin in the non-particle portion.
【００１３】樹脂基材Ｂは、紫外レーザの照射により除
去され易い粒子が表面部分に分散されている樹脂基材で
ある。この粒子は、必ずしも樹脂基材全体に含まれてい
る必要はなく、少なくとも粗化を行う領域（例えば、膜
形成用域）に含まれていればよく、普通、樹脂基材全体
１００重量％のうち粒子は１０〜９０重量％を占める。
この紫外レーザの照射により除去され易い粒子として
は、非粒子部分の樹脂より柔らかい軟質の樹脂粉末が挙
げられる。The resin base material B is a resin base material in which particles that are easily removed by irradiation with an ultraviolet laser are dispersed in the surface portion. The particles do not necessarily have to be contained in the entire resin base material, and may be contained in at least a roughening region (for example, a film forming region). Of these, particles account for 10 to 90% by weight.
Examples of the particles that are easily removed by irradiation with the ultraviolet laser include soft resin powder that is softer than the resin in the non-particle portion.
【００１４】樹脂基材Ｃは、紫外レーザの照射によって
も除去されにくい粒子と紫外レーザの照射により除去さ
れ易い粒子の両方の粒子が表面部分に分散されている樹
脂基材である。これらの粒子は、必ずしも樹脂基材全体
に含まれている必要はなく、少なくとも粗化を行う領域
（例えば、膜形成用域）に含まれていればよく、普通、
樹脂基材全体１００重量％のうち粒子は１０〜９０重量
％を占める。この場合、紫外レーザの照射に対する除去
性は、紫外レーザの照射により除去され易い粒子が一番
良く、紫外レーザの照射によっても除去され難い粒子が
一番悪く、非粒子部分の樹脂が両粒子の間となる。The resin base material C is a resin base material in which both the particles that are difficult to be removed by the irradiation of the ultraviolet laser and the particles that are easily removed by the irradiation of the ultraviolet laser are dispersed in the surface portion. These particles do not necessarily need to be contained in the entire resin base material, and may be contained in at least a roughening region (for example, a film forming region).
The particles account for 10 to 90% by weight of the total 100% by weight of the resin substrate. In this case, the removability with respect to the irradiation of the ultraviolet laser is the best particles that are easily removed by the irradiation of the ultraviolet laser, the particles that are difficult to be removed even by the irradiation of the ultraviolet laser are the worst, and the resin of the non-particle portion is Will be in between.
【００１５】樹脂基材Ｄは、一部表面部分を紫外レーザ
の照射により粗化されやすい樹脂材料で形成した樹脂基
材である。他の部分は紫外レーザによっても粗化され難
い樹脂材料からなる。基材表面の粗化を行う部分のみを
紫外レーザの照射により粗化されやすい樹脂材料で形成
しておくのである。樹脂基材Ｄは、粗化容易な樹脂材料
と粗化困難な樹脂材料を二色成形法などを用いて成形す
ることで簡単に作れる。The resin base material D is a resin base material whose surface is partially made of a resin material which is easily roughened by irradiation with an ultraviolet laser. The other part is made of a resin material that is not easily roughened by an ultraviolet laser. Only the portion of the surface of the base material that is to be roughened is made of a resin material that is easily roughened by irradiation with an ultraviolet laser. The resin substrate D can be easily made by molding a resin material that is easily roughened and a resin material that is difficult to be roughened using a two-color molding method or the like.
【００１６】樹脂基材Ｅは、基材表面に金属材料を分散
付着させた樹脂基材である。金属材料は粗化を行う領域
だけに分散付着させてもよいし全面に付着させてもよ
い。基材表面に対する金属材料の分散付着は、特定の方
法に限らないが、例えば、反射率の高い金属材料を無電
解めっきなどで部分的に分散析出させたり、粒径の小さ
な金属粒子（粉体）と有機溶剤との混合物（ペーストな
ど）を塗布し有機溶剤だけを飛ばして金属粒子を表面に
分散残留させたり、金属材料を蒸着（例えば、真空蒸
着）で部分的に分散付着させたりすることで行える。The resin base material E is a resin base material in which a metal material is dispersed and adhered to the surface of the base material. The metal material may be dispersed and adhered only to the roughening region, or may be adhered to the entire surface. Dispersion and attachment of the metal material to the surface of the base material is not limited to a specific method, but for example, a metal material having a high reflectance is partially dispersed and deposited by electroless plating, or a metal particle having a small particle size (powder) is used. ) And an organic solvent mixture (paste, etc.) and skipping only the organic solvent to disperse and leave the metal particles on the surface, or partially disperse and adhere the metal material by vapor deposition (for example, vacuum vapor deposition). Can be done with.
【００１７】樹脂基材Ｆは、表面部分に膜形成物質と結
合し易い物質が含まれている（通常は分散含有してい
る）樹脂基材である。この場合の表面部分には、事実
上、表面にのみに分散している形態を含む。樹脂基材Ａ
〜Ｆの粒子や物質は、表面付近の必要域に含まれていれ
ばよいが、基材全体に含まれていてもよい。また、上記
樹脂基材Ａ〜Ｅ中に膜形成物質と結合し易い物質を含ま
せる形態もある。膜形成物質と結合し易い物質として
は、めっき触媒、カップリング剤、膜形成物質と同じ物
質又は類似の物質（金属膜であれば同一の金属または類
似の金属に結合し易いのである）などが挙げられる。The resin base material F is a resin base material having a surface portion containing a substance that easily bonds to the film-forming substance (usually dispersed and contained). In this case, the surface portion includes a form in which the surface portion is dispersed only in the surface. Resin base material A
The particles and substances of to F may be contained in the necessary area near the surface, but may be contained in the entire substrate. In addition, there is also a mode in which the resin base materials A to E contain a substance that easily bonds to the film-forming substance. As the substance that easily binds to the film-forming substance, a plating catalyst, a coupling agent, the same substance as the film-forming substance or a similar substance (if it is a metal film, it is easy to bind to the same metal or a similar metal), etc. Can be mentioned.
【００１８】そして、上記の方法で粗化された基材表面
に対する膜の形成方法は、前述の如く、特定の方法に限
らない。紫外レーザの照射により基材表面の特定域であ
る膜形成用域だけを選択的に粗化しておき、膜の形成を
基材表面の特定域に選択的に行ったり、あるいは、膜を
基材表面の全面に施したあと、基材表面の特定域以外の
膜だけを除去するようにしたり、さらには、加えて、膜
の形成を反応性ガスの導入と同反応ガスへの光照射を伴
うＣＶＤにより膜形成を行うとともに、前記光照射によ
り基材表面の粗化面の加熱をも行うようにしたりしても
よい。The method of forming the film on the surface of the substrate roughened by the above method is not limited to a specific method as described above. Only the film formation area, which is a specific area on the substrate surface, is selectively roughened by irradiation with an ultraviolet laser and the film is selectively formed on the specific area on the substrate surface, or the film is formed on the substrate surface. After applying to the entire surface, only the film other than the specific area of the substrate surface should be removed, and in addition, the film formation involves the introduction of the reactive gas and the irradiation of the reaction gas with light. The film may be formed by CVD, and the roughened surface of the substrate surface may be heated by the light irradiation.
【００１９】膜形成用域の選択的粗化は、所定パターン
化のために基材表面の全面に形成しためっき膜の不要部
分の選択的除去に好都合である。めっき膜における粗化
域以外の除去する部分の下が粗化されておらず密着力が
弱く剥がれ易く残留しないからである。除去するめっき
膜の下も粗化される全面粗化では、絶縁低下の原因とな
る残留めっき膜が残り易くなる。残留めっき膜が残らな
いように過剰な条件でエッチングを行うと、残るめっき
膜部分にサイドエッチが起こり易くなる。The selective roughening of the film forming area is convenient for the selective removal of unnecessary portions of the plating film formed on the entire surface of the substrate for forming the predetermined pattern. This is because the area under the removed portion other than the roughened area in the plating film is not roughened, the adhesive strength is weak, and peeling easily occurs and does not remain. In the roughening of the entire surface in which the plating film to be removed is also roughened, a residual plating film that causes insulation deterioration tends to remain. If etching is performed under excessive conditions so that the residual plating film does not remain, side etching easily occurs in the remaining plating film portion.
【００２０】さらに、この発明の基材表面の粗化から膜
の形成までの具体的な処理例を、図２〜７を参照しなが
ら説明する。図２〜７では、最終的に特定パターンの導
電膜２を有するプリント配線板を得ている。図２の処理
例では、紫外レーザによる粗化は基材１の表面全面に行
い、無電解めっき、電気めっきを基材表面の全面に施
し、レジストマスクを設け、選択的エッチングで不要部
分を除去し、特定パターンの導電膜２を基材１の表面に
形成する。核付けの前に、粗化された基材１の表面を光
照射により加熱し、粗化面の凸部の先端を球状化し太く
するのもよい。湿式粗化を用いずとも、導電膜２の密着
力が向上する。Further, specific processing examples from the roughening of the surface of the base material to the formation of the film of the present invention will be described with reference to FIGS. 2 to 7, a printed wiring board having the conductive film 2 having a specific pattern is finally obtained. In the processing example of FIG. 2, roughening by an ultraviolet laser is performed on the entire surface of the substrate 1, electroless plating and electroplating are performed on the entire surface of the substrate, a resist mask is provided, and unnecessary portions are removed by selective etching. Then, the conductive film 2 having a specific pattern is formed on the surface of the base material 1. Prior to the nucleation, the roughened surface of the base material 1 may be heated by light irradiation to make the tip of the convex portion of the roughened surface spherical and thick. The adhesion of the conductive film 2 is improved without using wet roughening.
【００２１】図３の処理例では、紫外レーザによる粗化
は基材１の全面ではなく特定パターンの導電膜を設ける
膜形成用域のみに行い、無電解めっきを膜形成用域のみ
に選択的に析出形成した後、基材表面を光照射により加
熱し、粗化面の凸部の先端を球状化し先端のみを太くし
てアンカー効果を発揮させられるようになったり、ある
いは、無電解めっき膜と基材１の混合域を形成させるよ
うにして無電解めっき膜と基材１の密着力を高め、その
後、無電解めっき膜の上に電気めっき膜を積層し、特定
パターンの導電膜２を基材１の表面に形成する。湿式粗
化を用いずとも、レジストマスク形成や選択的エッチン
グの省略が出来、導電膜２の密着力も向上する。In the processing example of FIG. 3, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming area where the conductive film having a specific pattern is provided, and the electroless plating is selectively performed only on the film forming area. After depositing and forming on the substrate, the base material surface is heated by light irradiation to make the tip of the convex portion of the roughened surface spherical and thicken only the tip so that the anchor effect can be exhibited, or the electroless plating film The adhesion between the electroless plated film and the base material 1 is enhanced by forming a mixed area of the electroless plated film and the base material 1, and then the electroplated film is laminated on the electroless plated film to form the conductive film 2 having a specific pattern. It is formed on the surface of the base material 1. The resist mask formation and selective etching can be omitted without using wet roughening, and the adhesion of the conductive film 2 is improved.
【００２２】図４の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行うが、粗化
用の紫外レーザを、反応ガスの導入と同反応ガスへのレ
ーザ照射を伴うレーザＣＶＤの前記反応ガスへの照射レ
ーザとしても用い、基材表面に対し粗化と同時にレーザ
ＣＶＤにより金属膜の形成を膜形成用域のみに行う。そ
して、金属膜の上に電気めっき膜を積層し、特定パター
ンの導電膜２を基材１の表面に形成している。湿式粗化
を用いず、レジストマスク形成や選択的エッチングの省
略が出来、導電膜２の密着力も向上する。In the processing example of FIG. 4, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming region. However, the roughening ultraviolet laser is used to introduce the reaction gas into the reaction gas. It is also used as a laser for irradiating the above reaction gas in laser CVD accompanied by laser irradiation, and a metal film is formed only in the film formation region by laser CVD at the same time as roughening the surface of the substrate. Then, an electroplating film is laminated on the metal film to form the conductive film 2 having a specific pattern on the surface of the base material 1. The resist mask formation and the selective etching can be omitted without using the wet roughening, and the adhesion of the conductive film 2 is improved.
【００２３】図５の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行い、無電解
めっき、電気めっきを基材表面の全面に施し、レジスト
マスクを設け、選択的エッチングで不要部分を除去し、
特定パターンの導電膜２を基材１の表面に形成してい
る。核付けの前に、粗化された基材１の表面を光照射に
より加熱し、粗化面の凸部の先端を球状化し先端のみを
太くしてアンカー効果を発揮させられるようにしておく
のもよい。湿式粗化を用いず、選択的エッチングは、非
粗化面の上の膜を除去するのであるから容易であり、導
電膜２の密着力も向上する。In the processing example of FIG. 5, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming area, and electroless plating and electroplating are performed on the entire surface of the substrate to provide a resist mask. , Remove unnecessary parts by selective etching,
The conductive film 2 having a specific pattern is formed on the surface of the base material 1. Before nucleating, the surface of the roughened substrate 1 is heated by light irradiation, and the tip of the convex portion of the roughened surface is made spherical so that only the tip is thickened so that the anchor effect can be exhibited. Good. Selective etching is easy because the film on the non-roughened surface is removed without using wet roughening, and the adhesion of the conductive film 2 is also improved.
【００２４】図６の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行い、核付け
を行ったのち、洗浄等で非粗化域の核剤を除去してか
ら、無電解めっきを行い、膜形成用域のみにめっき膜を
析出形成した後、無電解めっき膜の上に電気めっき膜を
積層し、特定パターンの導電膜２を基材１の表面に形成
している。湿式粗化を用いずとも、レジストマスク形成
や選択的エッチングの省略が出来、導電膜２の密着力も
向上する。In the processing example of FIG. 6, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming region, and after nucleating, the nucleating agent in the non-roughening region is removed by washing or the like. After that, electroless plating is performed to deposit and form a plating film only on the film forming area, and then an electroplating film is laminated on the electroless plating film to form the conductive film 2 having a specific pattern on the surface of the substrate 1. Is formed. The resist mask formation and selective etching can be omitted without using wet roughening, and the adhesion of the conductive film 2 is improved.
【００２５】図７の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行い、その
後、反応性ガスの導入と同反応ガスへの光照射を伴うＣ
ＶＤ（レーザ熱ＣＶＤなど）により行うとともに前記光
照射により基材表面の粗化面の加熱を行うようにして、
膜形成用域のみに金属膜を形成する。光照射の加熱によ
り金属膜は、基材と混合域を形成したり、粗化面の凸部
先端が球状化したりするため、基板に強く密着する。そ
して、この金属膜の上に電気めっき膜を積層し、特定パ
ターンの導電膜２を基材１の表面に形成する。湿式粗化
を用いずとも、無電解めっきやレジストマスク形成や選
択的エッチングの省略が出来、導電膜２の密着力も向上
する。In the processing example of FIG. 7, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming region, and thereafter, the reactive gas is introduced and the reaction gas is irradiated with light C.
VD (laser thermal CVD, etc.) and heating the roughened surface of the base material by the light irradiation,
A metal film is formed only in the film formation area. The heating of the light irradiation causes the metal film to form a mixed region with the base material and the tip of the convex portion of the roughened surface to be spherical, so that it strongly adheres to the substrate. Then, an electroplating film is laminated on the metal film to form the conductive film 2 having a specific pattern on the surface of the base material 1. Even without using wet roughening, electroless plating, formation of a resist mask, and selective etching can be omitted, and the adhesion of the conductive film 2 is improved.
【００２６】[0026]
【作用】この発明のパターン膜形成方法の場合、基材表
面に対し紫外レーザの照射により粗化を行うため、湿式
粗化を用いずに基材表面の粗化が実現できる。紫外レー
ザは十分なエネルギーを有するため、粗化面での凹みが
膜形成用域に機械的な粗化方法の場合よりも深くなり、
粗化された基材表面に形成される膜は密着力の十分なも
のとなる。In the pattern film forming method of the present invention, since the surface of the substrate is roughened by irradiation with an ultraviolet laser, the surface of the substrate can be roughened without using wet roughening. Since the ultraviolet laser has sufficient energy, the recess on the roughened surface becomes deeper in the film formation area than in the case of the mechanical roughening method,
The film formed on the roughened surface of the substrate has sufficient adhesion.
【００２７】粗化された基材表面を光照射により加熱す
る場合、粗化面の凸部の先端のみが太くアンカー効果が
備わったり、膜と基材の混在域が出来るなど膜の密着力
はより十分なものとなる。紫外レーザの照射を特定域に
選択的に行う場合は、特定域以外の領域に粗化面が形成
されないため、特定域への選択的膜形成が容易に行える
だけでなく、また、全面的に膜を形成してから膜形成域
以外の領域の膜を選択的に除く場合にも、除去する膜の
下が粗化されていないため容易に除去でき、特定域以外
の領域に膜が残ったり、特定域に残る膜のサイドエッチ
が防止できる。When the surface of the roughened substrate is heated by irradiation with light, only the tips of the convex portions of the roughened surface are thick and an anchor effect is provided, or a mixed region of the film and the substrate is formed, so that the adhesive force of the film is More than enough. When the ultraviolet laser irradiation is selectively applied to a specific area, a roughened surface is not formed in an area other than the specific area, so that not only selective film formation on the specific area can be easily performed, but Even when the film in the region other than the film formation region is selectively removed after the film is formed, it can be easily removed because the bottom of the film to be removed is not roughened, and the film remains in the region other than the specific region. The side etching of the film remaining in the specific area can be prevented.
【００２８】基材表面への紫外レーザを、反応ガスの導
入と同反応ガスへのレーザ照射を伴うレーザＣＶＤの前
記反応ガスへのレーザ照射として用い、基材表面に対し
粗化と同時にレーザＣＶＤによる膜形成をも行うと、粗
化と膜形成が同時に行える利点がある。紫外レーザの照
射によっても除去されにくい粒子が表面部分に分散され
ている樹脂基材に対し紫外レーザ照射を行うと、除去さ
れにくい粒子が突出残留した状態で粗化が行われる。粒
子の大きさや混合量の調節により深い凹みのある粗化が
できる。An ultraviolet laser is applied to the surface of the substrate as laser irradiation to the reaction gas of laser CVD accompanied by introduction of the reaction gas and laser irradiation to the reaction gas, and laser CVD is performed simultaneously with roughening of the surface of the substrate. If the film formation is also performed, there is an advantage that the roughening and the film formation can be performed at the same time. When ultraviolet irradiation is performed on a resin base material in which particles that are difficult to be removed by irradiation with an ultraviolet laser are dispersed on the surface portion, roughening is performed in a state in which particles that are difficult to be removed remain protruding. Roughening with deep dents can be achieved by adjusting the size of particles and the amount of mixture.
【００２９】紫外レーザの照射により除去され易い粒子
が表面部分に分散されている樹脂基材に対し紫外レーザ
照射を行うと、紫外レーザで除去され易い粒子が除かれ
凹みが表面に分散現出した状態となる。粒子の大きさや
混合量の調節により深い凹みの粗化ができる。紫外レー
ザの照射によっても除去されにくい粒子と、紫外レーザ
の照射により除去され易い粒子の両方の粒子が表面部分
に分散されている樹脂基材に対し紫外レーザ照射を行う
と、除去され難い粒子は突出残留するとともに除去され
易い粒子が除かれ凹みが表面に分散現出し、粗化が出来
る。やはり、粒子の大きさや混合量の調節により深い凹
みのある粗化ができる。Particles that are easily removed by irradiation with an ultraviolet laser are dispersed on the surface portion of the resin substrate. When ultraviolet laser irradiation is performed on the resin substrate, particles that are easily removed by the ultraviolet laser are removed and dents appear on the surface. It becomes a state. It is possible to roughen deep dents by adjusting the size and mixing amount of particles. Particles that are difficult to remove even by irradiation with an ultraviolet laser and particles that are easily removed by irradiation with an ultraviolet laser are subjected to ultraviolet laser irradiation on a resin substrate in which surface particles are dispersed. Particles that remain protruding and are easily removed are removed, and pits are dispersed and appear on the surface, allowing roughening. After all, roughening with deep depressions can be achieved by adjusting the size of particles and the amount of mixture.
【００３０】表面部分の一部を紫外レーザの照射により
粗化されやすい樹脂材料で形成した樹脂基材に対し、紫
外レーザ照射を行うと、紫外レーザ照射で粗化されやす
い樹脂材料の部分だけが選択的に粗化される。他の部分
が紫外レーザによっても粗化され難い樹脂材料で出来て
いる樹脂基材でも、基材表面の必要部分の選択的粗化が
可能となる。When ultraviolet laser irradiation is performed on a resin base material whose surface portion is partially made of a resin material that is easily roughened by irradiation with an ultraviolet laser, only a portion of the resin material that is easily roughened by ultraviolet laser irradiation is exposed. Selectively roughened. Even if the resin base material is made of a resin material that is hard to be roughened by the ultraviolet laser in the other portion, it is possible to selectively roughen the necessary portion of the base material surface.
【００３１】膜形成物質と結合し易い物質を表面部分に
含有する樹脂基材を用いると、粗化面で膜形成物質と結
合し易い物質が結合して膜の密着力がより高まる。金属
材料を表面に分散付着させた樹脂基材に対し紫外レーザ
を照射すると、金属材料の非付着域が選択的に除かれ深
い凹みが分散現出し十分な深さの粗化が出来る。When a resin base material containing a substance that easily binds to the film-forming substance on the surface portion is used, the substance that easily binds to the film-forming substance bonds on the roughened surface, and the adhesion of the film is further enhanced. When an ultraviolet laser is irradiated to a resin base material on which a metal material is dispersed and adhered on the surface, a non-adhesive area of the metal material is selectively removed, and deep dents are exposed and roughening can be performed to a sufficient depth.
【００３２】この発明の表面粗化方法により基材表面の
特定域が選択的に粗化された基材を用いる場合、特定域
以外の領域が粗化されていないため、特定域への選択的
な膜形成や、膜形成用域以外の領域上の膜の除去が容易
に行え、特定域だけへサイドエッチのない膜を設けるこ
とが容易に行える。加えて、膜形成を、反応性ガスの導
入と同反応性ガスに対する光照射を伴うＣＶＤにより行
うと同時に光照射により基材表面の粗化面の加熱をも行
う場合、粗化面の凸部の先端が太くなったり、膜と基材
の混在域が出来るなど膜の密着力はより十分なものとな
る。When a base material in which a specific area on the surface of the base material is selectively roughened by the surface roughening method of the present invention is used, since the area other than the specific area is not roughened, the selective area to the specific area is selected. It is possible to easily form a film and remove a film on a region other than the film formation region, and to easily form a film without side etching only on a specific region. In addition, when the film formation is performed by the CVD with the introduction of the reactive gas and the light irradiation to the reactive gas, the roughened surface of the base material surface is also heated by the light irradiation, when the convex portion of the roughened surface is used. The tip has a thicker end, and a mixed region of the film and the base material is formed, so that the adhesive force of the film becomes more sufficient.
【００３３】[0033]
【実施例】以下、この発明の実施例について説明する。
この発明は、下記の実施例に限らない。 −実施例１− 実施例１では、図８にみるように、基材１の表面の膜形
成用域のみに紫外レーザを照射して選択的に粗化し、図
６の処理例に従って、無電解めっき、電気めっきを施
し、特定パターンの導電膜２を基材１の表面に形成す
る。勿論、粗化のあと、図５の処理例に従って、無電解
めっき、電気めっきを施し、選択エッチングし、特定パ
ターンの導電膜２を基材１の表面に形成してもよい。無
電解めっきは銅めっき、ニッケルめっき、金めっき等が
あり、電気めっきにも、銅めっき、ニッケルめっき、金
めっき等がある。Embodiments of the present invention will be described below.
The present invention is not limited to the embodiments described below. -Example 1-In Example 1, as shown in FIG. 8, only the film forming area on the surface of the substrate 1 was irradiated with an ultraviolet laser to be selectively roughened, and electroless according to the processing example of FIG. The conductive film 2 having a specific pattern is formed on the surface of the base material 1 by performing plating and electroplating. Of course, after roughening, electroless plating, electroplating, and selective etching may be performed to form the conductive film 2 having a specific pattern on the surface of the substrate 1 according to the processing example of FIG. Electroless plating includes copper plating, nickel plating, gold plating and the like, and electroplating also includes copper plating, nickel plating, gold plating and the like.
【００３４】基材１には、ポリイミド、エポキシなどの
樹脂基材、金属基材、アルミナなどのセラミック基材な
ど何でもよい。紫外レーザの波長は１９３〜４００ｎｍ
程度、エネルギーは０．１〜１．０Ｊ／ｃｍ2 程度でよ
い。例えば、基材１が液晶ポリマー基材であれば、約
０．５〜０．７ｋｇ／ｃｍのピール強度がある。粗化し
ない場合の約０．０８ｋｇ／ｃｍのピール強度に比べて
格段の向上である。The base material 1 may be any material such as a resin base material such as polyimide or epoxy, a metal base material, or a ceramic base material such as alumina. The wavelength of the ultraviolet laser is 193-400 nm
The energy may be about 0.1 to 1.0 J / cm 2 . For example, if the substrate 1 is a liquid crystal polymer substrate, it has a peel strength of about 0.5 to 0.7 kg / cm. This is a marked improvement over the peel strength of about 0.08 kg / cm without roughening.
【００３５】具体的に、厚み１．６ｍｍのＡＢＳ樹脂
（アクリロニトリル・ブタジエン・スチレン共重合体系
樹脂）製基材１に波長２４８ｎｍ、エネルギー０．３Ｊ
／ｃｍ 2 の紫外レーザを照射し、粗化した後、無電解銅
めっき、ついで、電気銅めっきを行いプリント配線板を
得た。実施例１の場合、湿式粗化不要により問題の薬液
洗浄などがなくなり、基材表面の選択粗化が可能なため
特定パターンの導電膜２のサイドエッチの心配もなく、
導電膜２の密着力も高い。Specifically, an ABS resin having a thickness of 1.6 mm
(Acrylonitrile-butadiene-styrene copolymer system
Resin) substrate 1 wavelength 248nm, energy 0.3J
/ Cm 2After irradiating it with an ultraviolet laser and roughening it, electroless copper
Plating, then electrolytic copper plating, and
Obtained. In the case of Example 1, since the wet roughening is not necessary, the chemical solution in question
Since there is no need for cleaning, selective roughening of the substrate surface is possible
There is no need to worry about side etching of the conductive film 2 with a specific pattern,
The adhesion of the conductive film 2 is also high.
【００３６】−実施例２− この発明では、図９の（ａ）にみるように、基材１全面
に紫外レーザを照射して粗化し、そのまま、図９の
（ｂ）にみるように、膜３を形成してもよいのである
が、図９の（ｃ）にみるように、基材１から膜３が剥が
れるのを十分に防ぐには、以下のようにするのがよい。
すなわち、図１０の（ａ）にみるように、基材１全面に
紫外レーザを照射して粗化し、ついで、図１０の（ｂ）
にみるように、粗化面に光照射による熱処理をし、粗化
面の細い凸部の先端のみを球状化し太くしてから、図１
０の（ｃ）にみるように、膜３を形成する。この後、図
２の処理例に準じて、特定パターンの例えば銅などの導
電膜２を基材１の表面に形成してもよい。Example 2 In this invention, as shown in FIG. 9 (a), the entire surface of the substrate 1 is irradiated with an ultraviolet laser to be roughened, and as it is seen in FIG. 9 (b), The film 3 may be formed, but as shown in (c) of FIG. 9, in order to sufficiently prevent the film 3 from peeling off from the base material 1, the following is preferable.
That is, as shown in FIG. 10A, the entire surface of the substrate 1 is irradiated with an ultraviolet laser to be roughened, and then, as shown in FIG.
As shown in Fig. 1, the roughened surface is subjected to heat treatment by light irradiation to make only the tip of the thin convex portion of the roughened surface spherical and thick, and then
As shown in 0 (c), the film 3 is formed. After that, a conductive film 2 of a specific pattern, such as copper, may be formed on the surface of the substrate 1 according to the processing example of FIG.
【００３７】基材１には、ＡＢＳ、ポリカーボネイト、
液晶ポリマー等の有機樹脂基材、Ａｌ2 Ｏ3 、ＳｉＯ2
等の酸化物系セラミックス基材、Ｃｕ、Ａｌ、Ｆｅ、Ｎ
ｉ、Ａｕ、Ａｇ等の金属基材など粗化後の光照射で凸部
の先端が溶ける又は軟化する材料の基材が適当である。
光照射は、ＣＯ2 レーザ、ＹＡＧレーザなどの赤外レー
ザや光ビーム（例えば、ＹＡＧレーザ第２高調波など）
等が挙げられる。The substrate 1 is made of ABS, polycarbonate,
Organic resin base material such as liquid crystal polymer, Al 2 O 3 , SiO 2
Oxide ceramic base materials such as Cu, Al, Fe, N
A base material made of a material, such as a metal base material such as i, Au, or Ag, in which the tip of the convex portion is melted or softened by irradiation with light after roughening is suitable.
Light irradiation is performed by an infrared laser such as a CO 2 laser or a YAG laser or a light beam (for example, a YAG laser second harmonic wave).
Etc.
【００３８】具体的に、厚み１．６ｍｍのＡＢＳ樹脂製
基材に波長２４８ｎｍ、エネルギー０．３Ｊ／ｃｍ2 の
紫外レーザを照射し、粗化した後、波長１０６４ｎｍ、
エネルギー０．１Ｊ／ｃｍ2 のＹＡＧレーザを照射し、
図２の処理例に従って、プリント配線板を得た。実施例
２の場合、湿式粗化不要で薬液洗浄などがなくなり、粗
化面の細い凸部の先端のみが太くてアンカー効果を発揮
するため、膜の密着力が非常によくなる。Specifically, an ABS resin substrate having a thickness of 1.6 mm is irradiated with an ultraviolet laser having a wavelength of 248 nm and an energy of 0.3 J / cm 2 to roughen it, and then a wavelength of 1064 nm,
Irradiate a YAG laser with energy of 0.1 J / cm 2 ,
A printed wiring board was obtained according to the processing example of FIG. In the case of Example 2, wet roughening is not required, chemical cleaning is eliminated, and only the tip of the convex portion having a thin roughened surface is thick to exert an anchoring effect, so that the adhesive force of the film becomes very good.
【００３９】−実施例３− 実施例３では、実施例２において、基材１に対する紫外
レーザを、図１１にみるように、膜形成用域のみに照射
し選択的に粗化し、粗化面に光照射を行い熱処理をし、
粗化面の細い凸部の先端のみを球状化して太くし、図５
の処理例に従って、プリント配線板を得た。Example 3 In Example 3, as in Example 2, the ultraviolet laser for the substrate 1 was irradiated only on the film forming region to selectively roughen the roughened surface, as shown in FIG. It is irradiated with light and heat treated,
Only the tip of the thin convex portion of the roughened surface is made spherical and thickened.
A printed wiring board was obtained according to the processing example of.
【００４０】膜形成用域以外の領域は非粗化であるた
め、無電解銅めっき膜と電気銅めっき膜の選択エッチン
グが容易であり、めっき膜の残留やサイドエッチも防止
できる。 −実施例４− 実施例４では、図１２にみるように、樹脂基材やセラミ
ック基材などの基材１を紫外レーザの照射により粗化し
てから、無電解めっき等により金属膜５を形成した後、
光照射による熱処理により、粗化面の凸部の先端に基材
と金属膜層の混合域を形成し金属膜の密着力を上げてい
る。Since the area other than the film forming area is not roughened, selective etching of the electroless copper plating film and the electrolytic copper plating film is easy, and the remaining plating film and side etching can be prevented. Example 4 In Example 4, as shown in FIG. 12, the substrate 1 such as a resin substrate or a ceramic substrate is roughened by irradiation with an ultraviolet laser, and then the metal film 5 is formed by electroless plating or the like. After doing
By heat treatment by light irradiation, a mixed region of the base material and the metal film layer is formed at the tip of the convex portion of the roughened surface to increase the adhesive force of the metal film.
【００４１】粗化は、基材表面の全面に行ってもよい
し、膜形成用域のみに行ってもよい。膜形成用域のみを
粗化する場合は図３の処理例に従ってプリント配線板を
得ることが出来るし、全面を粗化する場合は、光照射に
よる熱処理のあと従来のパターンニング方式によりプリ
ント配線板を得ることができる。金属膜５としては、
銅、金、ニッケル等の単一膜、あるいは、それらの積層
膜が挙げられる。単一膜としては無電解めっきによる金
属膜が挙げられ、積層膜としては、無電解めっきによる
金属膜に電気めっきによる金属膜を積層したものが挙げ
られる。熱処理用の光としては、ＹＡＧレーザ、ＣＯ2
レーザ、赤外線などが挙げられる。The roughening may be performed on the entire surface of the base material or only on the film forming area. When only the film forming area is roughened, the printed wiring board can be obtained according to the processing example of FIG. 3, and when the entire surface is roughened, the printed wiring board is subjected to the conventional patterning method after the heat treatment by light irradiation. Can be obtained. As the metal film 5,
A single film of copper, gold, nickel, or the like, or a laminated film thereof can be used. Examples of the single film include a metal film formed by electroless plating, and examples of the laminated film include a metal film formed by electroless plating and a metal film formed by electroplating. Light for heat treatment includes YAG laser, CO 2
Examples include lasers and infrared rays.
【００４２】実施例２の条件に準じて、図３の処理例に
したがってプリント配線板を得た。金属膜５の一部が、
いわば基材１中に埋め込まれた形となるため、密着強度
は大きい。 −実施例５− 実施例５では、図１３の（ａ）にみるように、基材１
を、チャンバ内に入れ、基材１の表面に対しウインドウ
より紫外レーザを照射しつつ紫外レーザＣＶＤによる粗
化と同時に膜の形成を行っている。紫外レーザＣＶＤ
は、基材１表面に反応性ガスの導入と同反応性ガスに対
する紫外レーザの照射を行い膜形成する方法であり、反
応ガスへの照射用紫外レーザと粗化用紫外レーザを兼用
している。反応性ガスとしては、Ａｌ（ＣＨ）3 ，Ｃｕ
（ＨＣＯＯ）2 ・２Ｈ2 Ｏ，Ｃｕヘキサフルオロアセチ
ルアセトネート，Ｎｉ（ＣＯ）4 等が挙げられる。A printed wiring board was obtained according to the processing example of FIG. 3 according to the conditions of Example 2. A part of the metal film 5
The adhesive strength is large because it is so-called embedded in the base material 1. Example 5 In Example 5, as shown in FIG. 13A, the base material 1
Is placed in a chamber, and while the surface of the substrate 1 is being irradiated with an ultraviolet laser from a window, the film is formed simultaneously with roughening by ultraviolet laser CVD. UV laser CVD
Is a method for forming a film by introducing a reactive gas onto the surface of the base material 1 and irradiating the reactive gas with an ultraviolet laser, and is used both as an ultraviolet laser for irradiating the reactive gas and as a roughening ultraviolet laser. . As the reactive gas, Al (CH) 3 , Cu
(HCOO) 2 .2H 2 O, Cu hexafluoroacetylacetonate, Ni (CO) 4 and the like.
【００４３】紫外レーザの照射は基材１の表面の全面で
も膜形成用域のみでもよい。紫外レーザが照射された領
域が粗化される。紫外レーザが照射される領域では、図
１３の（ｂ）にみるように、粗化と同時に膜形成用金属
粒子が凹部に析出し、膜は凹部内に入り込む形となるた
め、密着強度は十分なものとなる。紫外レーザのエネル
ギーは０．１〜１．０Ｊ／ｃｍ2 程度が適当である。Irradiation with the ultraviolet laser may be performed on the entire surface of the substrate 1 or only in the film forming area. The area irradiated with the ultraviolet laser is roughened. In the region irradiated with the ultraviolet laser, as shown in FIG. 13 (b), the metal particles for film formation are deposited in the recesses simultaneously with the roughening, and the film enters into the recesses, so that the adhesion strength is sufficient. It will be The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm 2 .
【００４４】厚み１．６ｍｍのＡＢＳ樹脂製基材に波長
２４８ｎｍ、エネルギー０．３Ｊ／ｃｍ2 の紫外レーザ
を用い、反応性ガスとしては、Ｃｕ（ＨＣＯＯ）2 ・２
Ｈ2Ｏを用い、図４の処理例に従ってプリント配線板を
得た。粗化と膜形成が同時であり、無電解めっき工程が
不要であり、粗化部分では金属膜と基材が混合した状態
となり、密着強度が高い。[0044] Using wavelength ABS resin substrate having a thickness of 1.6 mm 248 nm, the ultraviolet laser energy 0.3 J / cm 2, as the reactive gas, Cu (HCOO) 2 · 2
Using H 2 O, a printed wiring board was obtained according to the processing example of FIG. Roughening and film formation are performed at the same time, an electroless plating step is not required, and the metal film and the base material are mixed in the roughened portion, so that the adhesion strength is high.
【００４５】−実施例６− 実施例６では、図１４の（ａ）にみるように、紫外レー
ザの照射によっては除去されにくい粒子１１が表面部分
に分散されている樹脂基材Ａを用いる。粒子１１は、セ
ラミック、ガラス、テフロンなどであって０．５〜７０
μｍ程度の粒径のものが例示され、非粒子部分の樹脂と
しては、エポキシ、ポリイミド、ポリカーボネート樹脂
等が挙げられる。樹脂基材全体１００重量％のうち粒子
が１０〜９０重量％を占める。Example 6 In Example 6, as shown in FIG. 14A, the resin base material A in which the particles 11 which are difficult to be removed by the irradiation of the ultraviolet laser are dispersed in the surface portion is used. The particles 11 are ceramics, glass, Teflon, etc., and are 0.5 to 70.
The resin having a particle size of about μm is exemplified, and examples of the resin of the non-particle portion include epoxy resin, polyimide resin, and polycarbonate resin. The particles account for 10 to 90% by weight of the total 100% by weight of the resin substrate.
【００４６】そして、樹脂基材Ａに、図１４の（ｂ）に
みるように、紫外レーザを照射すると、粒子１１は突出
残留した状態となって粗化されることになる。紫外レー
ザの照射は、樹脂基材Ａの表面の全面でも膜形成用域の
みでもよい。全面を粗化し、所定パターンの導電膜を形
成する場合は、例えば、図２の処理例に従えばよい。膜
形成用域のみを粗化し、所定パターンの導電膜を形成す
る場合は、例えば、図５の処理例に従えばよい。Then, when the resin base material A is irradiated with an ultraviolet laser as shown in FIG. 14B, the particles 11 are left in a protruding state and roughened. The irradiation of the ultraviolet laser may be performed on the entire surface of the resin base material A or only in the film forming area. When the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. When only the film formation area is roughened to form a conductive film having a predetermined pattern, for example, the processing example of FIG. 5 may be followed.
【００４７】具体的には、エポキシ樹脂に０．５〜７０
μｍの粒径（平均粒径１０μｍ）のシリカ（ＳｉＯ2 ）
粉末を８５重量％混合した成形基材（一般の機器に用い
られる電子機器封止材料）を用い、波長２４８ｎｍの紫
外レーザを膜形成用域のみに照射して粗化し、図５の処
理例に従ってプリント配線板を得た。紫外レーザのエネ
ルギーは０．２〜０．５Ｊ／ｃｍ2 であった。Concretely, 0.5 to 70 is added to the epoxy resin.
Silica (SiO 2 ) with a particle size of μm (average particle size 10 μm)
Using a molding base material (electronic device sealing material used for general equipment) in which 85% by weight of powder is mixed, an ultraviolet laser having a wavelength of 248 nm is irradiated only to the film forming region for roughening, and according to the processing example of FIG. A printed wiring board was obtained. The energy of the ultraviolet laser was 0.2 to 0.5 J / cm 2 .
【００４８】湿式粗化で必須の問題の洗浄工程が不要で
工程簡略化が行え、基材表面に形成する金属膜の密着力
が向上する。 −実施例７− 実施例７では、図１５の上の図にみるように、紫外レー
ザの照射により除去され易い粒子１２が表面部分に分散
されている樹脂基材Ｂを用いる。粒子１２は、ポリイミ
ド等の樹脂粉末などであって０．５〜１００μｍ程度の
粒径のものが例示され、非粒子部分の樹脂としては、テ
フロン樹脂等が挙げられる。樹脂基材全体１００重量％
のうち粒子が１０〜９０重量％を占める。Since the washing step, which is an essential problem in wet roughening, is not required, the steps can be simplified and the adhesion of the metal film formed on the surface of the substrate is improved. -Example 7-In Example 7, the resin base material B in which the particles 12 which are easily removed by the irradiation of the ultraviolet laser are dispersed in the surface portion is used as shown in the upper diagram of FIG. The particles 12 are, for example, resin powder such as polyimide having a particle diameter of about 0.5 to 100 μm, and the non-particle portion resin includes Teflon resin and the like. 100% by weight of resin base material
Of these, particles account for 10 to 90% by weight.
【００４９】非粒子部分の樹脂と粒子１２の具体的な組
み合わせ例は以下の通りである。 組み合わせ 非粒子部分の樹脂：テフロン； 粒子１
２：ポリイミド、ポリカーボネート他、殆どの種類の樹
脂粒子； 組み合わせ 非粒子部分の樹脂：ポリカーボネート；
粒子１２：ポリイミド、ポリサルホンなどの樹脂粒
子； 組み合わせ 非粒子部分の樹脂：ポリサルホン； 粒
子１２：ポリイミドなどの樹脂粒子； そして、樹脂基材Ｂに、図１５の下の図にみるように、
紫外レーザを照射すると、粒子１２は除かれ凹みが表面
に分散現出し状態となって粗化されることになる。粒子
１２と非粒子部分の除去速度（エッチングレート）が異
なるため、エッチングレートの速い粒子１２が優先的に
除去される形で粗化が出来るのである。紫外レーザのエ
ネルギーは０．１〜１．０Ｊ／ｃｍ2 程度が適当であ
る。Specific examples of combinations of the non-particle portion resin and the particles 12 are as follows. Combination Non-particulate resin: Teflon; Particle 1
2: Polyimide, polycarbonate, and other types of resin particles; Combination non-particulate resin: polycarbonate;
Particles 12: Resin particles such as polyimide and polysulfone; Combination non-particle resin: Polysulfone; Particles 12: Resin particles such as polyimide; And on the resin base material B, as shown in the lower diagram of FIG.
Upon irradiation with an ultraviolet laser, the particles 12 are removed and the dents are dispersed and exposed on the surface to be roughened. Since the removal rates (etching rates) of the particles 12 and the non-particle portions are different, it is possible to roughen the particles 12 having a high etching rate preferentially. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm 2 .
【００５０】紫外レーザの照射は、樹脂基材Ｂの表面の
全面でも膜形成用域のみでもよい。全面を粗化し、所定
パターンの導電膜を形成する場合は、例えば、図２の処
理例に従えばよい。膜形成用域のみを粗化し、所定パタ
ーンの導電膜を形成する場合は、例えば、図５の処理例
に従えばよい。具体的には、テフロン（四フッ化エチレ
ン系樹脂）に、粒径５０μｍのポリイミド粉末を３０重
量％混合した成形基材を用い、波長２４８ｎｍの紫外レ
ーザを膜形成用域のみに照射して粗化し、図５の処理例
に従ってプリント配線板を得た。紫外レーザのエネルギ
ーは０．３Ｊ／ｃｍ2 であった。The irradiation of the ultraviolet laser may be performed on the entire surface of the resin base material B or only in the film forming area. When the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. When only the film formation area is roughened to form a conductive film having a predetermined pattern, for example, the processing example of FIG. 5 may be followed. Specifically, using a molding base material in which Teflon (tetrafluoroethylene resin) is mixed with 30% by weight of polyimide powder having a particle size of 50 μm, an ultraviolet laser having a wavelength of 248 nm is irradiated only on the film forming region to roughen the film. Then, a printed wiring board was obtained according to the processing example of FIG. The energy of the ultraviolet laser was 0.3 J / cm 2 .
【００５１】湿式粗化で必須の問題の洗浄工程が不要で
工程簡略化が行え、基材表面に形成する金属膜の密着力
が向上する。 −実施例８− 実施例８では、図１６の（ａ）にみるように、紫外レー
ザの照射によっても除去されにくい粒子１１と紫外レー
ザの照射により除去され易い粒子１２の両方が表面に分
散されている樹脂基材Ｃを用いる。粒子１１は、セラミ
ック、ガラス、テフロンなどであって０．５〜１００μ
ｍ程度の粒径のものが例示され、粒子１２は、ポリイミ
ド等の樹脂粉末などであって０．５〜１００μｍ程度の
粒径のものが例示される。非粒子部分の樹脂としては、
ポリカーボネート樹脂等が挙げられる。樹脂基材全体１
００重量％のうち粒子１１，１２が１０〜９０重量％を
占める。Since the washing step, which is an essential problem in wet roughening, is not required, the step can be simplified and the adhesion of the metal film formed on the surface of the substrate is improved. Example 8 In Example 8, as shown in FIG. 16A, both particles 11 that are difficult to remove by irradiation with an ultraviolet laser and particles 12 that are easily removed by irradiation with an ultraviolet laser are dispersed on the surface. The resin base material C is used. The particles 11 are ceramics, glass, Teflon, etc. and are 0.5 to 100 μm.
The particles 12 have a particle size of about m, and the particles 12 are resin powder such as polyimide and the like having a particle size of about 0.5 to 100 μm. As the resin of the non-particle part,
Examples include polycarbonate resins. Entire resin base material 1
Particles 11 and 12 occupy 10 to 90% by weight out of 00% by weight.
【００５２】そして、樹脂基材Ｃに、図１６の（ｂ）に
みるように、紫外レーザを照射すると、粒子１１は表面
に残留突出するとともに粒子１２は除かれ凹みが表面に
分散現出し状態となって粗化されることになる。粒子１
１，１２および非粒子部分の樹脂の材料は、除去速度
（エッチングレート）は粒子１１が最も遅く、粒子１２
が最も速く、非粒子部分の樹脂が両者の中間となるよう
に選定する。エッチングレートの差で粗化が出来るから
である。紫外レーザのエネルギーは０．１〜１．０Ｊ／
ｃｍ2 程度が適当である。Then, as shown in FIG. 16B, when the resin substrate C is irradiated with an ultraviolet laser, the particles 11 remain projected on the surface and the particles 12 are removed, and the recesses are dispersed and exposed on the surface. Will be roughened. Particle 1
The removal rate (etching rate) of the resin materials 1 and 12 and the non-particle portion of the resin is the slowest for the particles 11 and
Is the fastest, and the resin in the non-particulate portion is in the middle of the two. This is because roughening can be performed by the difference in etching rate. The energy of the ultraviolet laser is 0.1-1.0 J /
cm 2 is suitable.
【００５３】紫外レーザの照射は、樹脂基材Ｃの表面の
全面でも膜形成用域のみでもよい。全面を粗化し、所定
パターンの導電膜を形成する場合は、例えば、図２の処
理例に従えばよい。膜形成用域のみを粗化し、所定パタ
ーンの導電膜を形成する場合は、例えば、図５の処理例
に従えばよい。具体的には、実施例６で用いた粒子１１
と実施例７で用いた粒子１２をテフロンに合計で３０重
量％混合した成形基材を用い、波長２４８ｎｍの紫外レ
ーザを膜形成用域のみに照射して粗化し、図５の処理例
に従ってプリント配線板を得た。紫外レーザのエネルギ
ーは０．３Ｊ／ｃｍ2 であった。The irradiation of the ultraviolet laser may be performed on the entire surface of the resin base material C or only in the film forming area. When the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. When only the film formation area is roughened to form a conductive film having a predetermined pattern, for example, the processing example of FIG. 5 may be followed. Specifically, the particles 11 used in Example 6 were used.
And the particles 12 used in Example 7 are mixed with Teflon in a total amount of 30% by weight, an ultraviolet laser having a wavelength of 248 nm is irradiated only to the film forming region for roughening, and printing is performed according to the processing example of FIG. The wiring board was obtained. The energy of the ultraviolet laser was 0.3 J / cm 2 .
【００５４】湿式粗化で必須の問題の洗浄工程が不要で
工程簡略化が行え、基材表面に形成する金属膜の密着力
が向上する。 −実施例９− 実施例９では、図１７の（ａ）にみるように、紫外レー
ザの照射により粗化されやすい樹脂材料１４で表面部分
の一部を形成し他の部分は紫外レーザでも粗化され難い
樹脂材料（基材樹脂）１５で形成した樹脂基材Ｄを用い
る。図１７の（ａ）にみるように、基材表面の粗化を行
う部分のみ樹脂材料１４としておけばよい。樹脂基材Ｄ
は、図１８にみるように、粗化容易な樹脂材料１４と粗
化困難な樹脂材料１５とを二色成形などを用いて複合化
することで簡単に作製することができる。Since the washing step, which is an essential problem in wet roughening, is not required, the step can be simplified and the adhesion of the metal film formed on the surface of the base material is improved. -Example 9-In Example 9, as shown in FIG. 17A, a part of the surface portion is formed by the resin material 14 that is easily roughened by irradiation with an ultraviolet laser, and the other portion is roughened by the ultraviolet laser. A resin base material D formed of a resin material (base material resin) 15 that is difficult to be converted is used. As shown in FIG. 17A, the resin material 14 may be used only in the portion where the surface of the base material is roughened. Resin base material D
As shown in FIG. 18, the resin can be easily manufactured by compounding the resin material 14 that is easily roughened and the resin material 15 that is difficult to be roughened using two-color molding or the like.
【００５５】樹脂材料１４としては、ポリイミドなどが
挙げられ、樹脂材料１５としては、液晶ポリマーやテフ
ロンなどが挙げられる。そして、樹脂基材Ｄに、図１７
の（ｂ）にみるように、紫外レーザを照射すると、樹脂
材料１４の表面が選択的に粗化される。つまり、膜形成
用域部分だけを樹脂材料１４で形成しておくと、自動的
に膜形成用域の選択粗化が出来るのである。紫外レーザ
のエネルギーは０．１〜１．０Ｊ／ｃｍ2 程度が適当で
ある。紫外レーザの照射は、樹脂基材Ｄの表面の全面で
も樹脂材料１４の表面のみでもよい。所定パターンの導
電膜を形成する場合は、例えば、図５または図６の処理
例に従えばよい。The resin material 14 may be polyimide or the like, and the resin material 15 may be liquid crystal polymer or Teflon. Then, as shown in FIG.
As shown in (b) of FIG. 3, when the ultraviolet laser is irradiated, the surface of the resin material 14 is selectively roughened. That is, if only the film forming area is formed of the resin material 14, the film forming area can be automatically roughened selectively. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm 2 . Irradiation with the ultraviolet laser may be performed on the entire surface of the resin substrate D or only the surface of the resin material 14. When the conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 5 or 6 may be followed.
【００５６】具体的には、樹脂材料１４をポリイミドと
し、樹脂材料１５をテフロンとする二色成形基材を用
い、波長２４８ｎｍの紫外レーザを照射して粗化し、図
６の処理例に従ってプリント配線板を得た。紫外レーザ
のエネルギーは０．２Ｊ／ｃｍ 2 であった。金型でもっ
て樹脂材料１４を必要域に選択的に配置し粗化するた
め、不要域には粗化が付きにくく、無電解めっき時にめ
っき不要域に膜が付きにくくなる。Specifically, the resin material 14 is made of polyimide.
And use a two-color molding base material in which the resin material 15 is Teflon.
Roughened by irradiating an ultraviolet laser with a wavelength of 248 nm.
A printed wiring board was obtained according to the processing example of No. 6. Ultraviolet laser
Energy is 0.2 J / cm 2Met. With mold
To dispose the resin material 14 selectively in the required area for roughening.
As a result, roughening is less likely to occur in unnecessary areas, and
The film is less likely to attach to unnecessary areas.
【００５７】−実施例１０− 実施例１０では、図１９の（ａ）にみるように、膜形成
物質と結合（物理的結合ないし化学的結合）し易い物質
１８が表面部分に含まれている（勿論、全体に含まれて
いてもよい）樹脂基材Ｆを用いる。膜形成物質と結合し
易い物質としては、めっき触媒、カップリング剤（γ−
アミノプロピルトリエトキシシラン等）、膜形成物質と
同じ物質又は類似の物質（金属膜であれば同一の金属又
は類似の金属：これであれば結合し易いのである）など
が挙げられる。母材樹脂としては、液晶ポリマー、ＡＢ
Ｓ樹脂、ポリカーボネート樹脂などが挙げられる。-Embodiment 10-In Embodiment 10, as shown in FIG. 19A, the surface portion contains a substance 18 that is easily bonded (physical bond or chemical bond) to the film-forming substance. The resin base material F (which may of course be included in the whole) is used. Examples of substances that easily bond with the film-forming substance include plating catalysts and coupling agents (γ-
Aminopropyltriethoxysilane, etc.), the same substance as the film-forming substance or a similar substance (the same metal or a similar metal in the case of a metal film: if this is the case, it is easy to bond). As the base resin, liquid crystal polymer, AB
Examples thereof include S resin and polycarbonate resin.
【００５８】実施例１０では、図１９の（ｂ）にみるよ
うに、紫外レーザを照射すると、樹脂基材Ｆの表面が粗
化されるとともに物質１８が露出するため、図１９の
（ｃ）にみるように、無電解めっき等で形成した金や
銅、ニッケル等のめっき膜は物質１８と結合し、粗化と
ともに密着力向上に寄与することになる。紫外レーザの
エネルギーは０．１〜１．０Ｊ／ｃｍ2 程度が適当であ
る。紫外レーザの照射は、樹脂基材Ｆの表面の全面でも
膜形成用域のみでもよい。全面を粗化し、所定パターン
の導電膜を形成する場合は、例えば、図２の処理例に従
えばよい。膜形成用域のみを粗化し、所定パターンの導
電膜を形成する場合は、例えば、図５または図６の処理
例に従えばよい。In Example 10, as shown in FIG. 19B, when the ultraviolet laser was irradiated, the surface of the resin base material F was roughened and the substance 18 was exposed, so that FIG. As will be seen from the above, the plating film of gold, copper, nickel or the like formed by the electroless plating or the like binds to the substance 18 and contributes to the roughening and the improvement of the adhesion. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm 2 . The irradiation of the ultraviolet laser may be performed on the entire surface of the resin base material F or only in the film forming area. When the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. When only the film formation area is roughened to form a conductive film having a predetermined pattern, for example, the processing example of FIG. 5 or 6 may be followed.
【００５９】具体的には、母材樹脂用のＡＢＳ樹脂に物
質１８として銅粉末を添加混合した成形基材を用い、波
長２４８ｎｍの紫外レーザを膜形成用域のみに照射して
粗化し、図６の処理例に従ってプリント配線板を得た。
紫外レーザのエネルギーは０．３Ｊ／ｃｍ2 であった。
湿式粗化が不要であるとともに、無電解めっきの場合の
核付け工程も省略できるようになる。Specifically, using a molding base material in which copper powder was added and mixed as a substance 18 to an ABS resin for a base material resin, an ultraviolet laser having a wavelength of 248 nm was irradiated to only a film forming region for roughening, A printed wiring board was obtained according to the processing example of No. 6.
The energy of the ultraviolet laser was 0.3 J / cm 2 .
No wet roughening is required, and the nucleation step in the case of electroless plating can be omitted.
【００６０】−実施例１１− 実施例１１では、図２０の（ａ）にみるように、基材表
面に金属材料２０を分散付着させた樹脂基材Ｅを用い
る。樹脂の種類はこれまでに例示したものが使える。金
属材料２０としては、銅、ニッケル、金、銀など紫外レ
ーザに対する反射率の高いものが好ましいが、これら例
示のものに限らない。金属材料２０の分散付着は、金属
めっき、金属粉体付着、金属材蒸着などの方法がある。Example 11 In Example 11, as shown in FIG. 20 (a), a resin base material E in which the metal material 20 is dispersed and adhered to the surface of the base material is used. As the type of resin, those exemplified so far can be used. The metal material 20 is preferably a material having a high reflectance with respect to an ultraviolet laser, such as copper, nickel, gold, or silver, but is not limited to these examples. Dispersion and attachment of the metal material 20 includes methods such as metal plating, metal powder attachment, and metal material vapor deposition.
【００６１】金属めっきの場合、無電解めっきのめっき
時間やめっき液の濃度の調整により、全面でなく部分的
めっきの範囲にめっきを止める。各部分めっきの大きさ
が０．５〜５μｍ程度となるようにする。金属粉体付着
の場合、粒径１０〜１００μｍ程度の粉体と、有機溶剤
（例えば、アセトン、アルコール等）の混合物（ペース
ト等）を塗布し、溶剤を飛ばして金属粉体を表面に残
す。混合物の粉体濃度は、塗布した際に粉体が基材表面
を覆い尽さない濃度に設定する。In the case of metal plating, the plating is stopped not in the entire surface but in the range of partial plating by adjusting the plating time of electroless plating and the concentration of the plating solution. The size of each partial plating is set to about 0.5 to 5 μm. In the case of metal powder adhesion, a mixture (paste or the like) of a powder having a particle size of about 10 to 100 μm and an organic solvent (eg, acetone, alcohol, etc.) is applied, and the solvent is blown to leave the metal powder on the surface. The powder concentration of the mixture is set to a concentration at which the powder does not completely cover the surface of the base material when applied.
【００６２】金属材蒸着の場合、蒸着初期は金属が点在
した状態となることを利用しており、基材全面が覆われ
る前に蒸着を停止し、全面でなく部分的蒸着の範囲に止
める。各部分蒸着の大きさが０．０１〜１μｍ程度が好
ましい。金属材料２０の分散付着の方法の選択で粗度の
調整が可能となる。実施例１１では、図２０の（ｂ）に
みるように、紫外レーザを照射すると、金属材料２０未
着部分の母材樹脂部分が選択的に除かれ深く掘られて粗
化が出来る。In the case of vapor deposition of a metal material, the fact that the metal is scattered in the initial stage of vapor deposition is utilized. The vapor deposition is stopped before the entire surface of the substrate is covered, and is stopped within the range of partial vapor deposition instead of the entire surface. . The size of each partial vapor deposition is preferably about 0.01 to 1 μm. The roughness can be adjusted by selecting the method of dispersion and adhesion of the metal material 20. In the eleventh embodiment, as shown in FIG. 20B, when the ultraviolet laser is irradiated, the base material resin portion where the metal material 20 is not adhered is selectively removed and deeply dug to roughen.
【００６３】紫外レーザのエネルギーは０．１〜１．０
Ｊ／ｃｍ2 程度が適当である。紫外レーザの照射は、樹
脂基材Ｅの表面の全面でも膜形成用域のみでもよい。全
面を粗化し、所定パターンの導電膜を形成する場合は、
例えば、図２の処理例に従えばよい。膜形成用域のみを
粗化し、所定パターンの導電膜を形成する場合は、例え
ば、図５の処理例に従えばよい。The energy of the ultraviolet laser is 0.1 to 1.0.
About J / cm 2 is suitable. Irradiation with the ultraviolet laser may be performed on the entire surface of the resin substrate E or only in the film forming area. When roughening the entire surface and forming a conductive film of a predetermined pattern,
For example, the processing example of FIG. 2 may be followed. When only the film formation area is roughened to form a conductive film having a predetermined pattern, for example, the processing example of FIG. 5 may be followed.
【００６４】具体的には、ＡＢＳ樹脂基材の表面に金属
粉体付着方法で金属材料２０を分散付着させた樹脂基材
に波長２４８ｎｍの紫外レーザを膜形成用域のみに照射
して粗化し、図５の処理例に従ってプリント配線板を得
た。紫外レーザのエネルギーは０．５Ｊ／ｃｍ2 であっ
た。金属材料２０の付着量の調整で表面粗度の調整が可
能である。Specifically, the resin base material, on which the metal material 20 is dispersed and adhered to the surface of the ABS resin base material by the metal powder adhesion method, is irradiated with an ultraviolet laser having a wavelength of 248 nm only in the film forming region to roughen it. A printed wiring board was obtained according to the processing example of FIG. The energy of the ultraviolet laser was 0.5 J / cm 2 . The surface roughness can be adjusted by adjusting the adhesion amount of the metal material 20.
【００６５】−実施例１２− 実施例１２では、図２１にみるように、基材１の表面の
膜形成用域（回路パターンに相当）のみに紫外レーザを
照射し、基材表面の膜形成用域のみを粗化し、無電解め
っき用の核（Ｐｄ等）付けを全面にしてから洗浄するこ
とにより、粗化面のみに核剤を残留させた後、無電解め
っきおよび電気めっきを行い、所定パターンの導電膜２
を膜形成用域のみに選択的に形成し、プリント配線板を
得る。-Example 12-In Example 12, as shown in FIG. 21, only the film forming area (corresponding to a circuit pattern) on the surface of the substrate 1 was irradiated with an ultraviolet laser to form a film on the substrate surface. By roughening only the application area and leaving the core (Pd etc.) for electroless plating on the entire surface and then washing to leave the nucleating agent only on the roughened surface, electroless plating and electroplating are performed, Conductive film 2 with a predetermined pattern
Is selectively formed only in the film forming area to obtain a printed wiring board.
【００６６】未粗化面に付着した核剤よりも粗化面の凹
部に入った核剤は洗浄で除去され難いことを利用してレ
ジストマスク無しで導電膜の選択形成を行うのである。
基材は、液晶ポリマー、ポリイミド、エポキシ等の樹脂
基材あるいはアルミナ等のセラミック基材など、これま
でに例示したものが使えるし、粗化に関しても、前述の
膜形成用域のみの粗化のいずれのものでも利用可能であ
る。Since the nucleating agent that has entered the concave portion of the roughened surface is more difficult to remove by washing than the nucleating agent that adheres to the unroughened surface, the conductive film is selectively formed without a resist mask.
As the base material, liquid crystal polymer, resin base material such as polyimide or epoxy, or ceramic base material such as alumina can be used, and the roughening can be performed only in the film forming area described above. Either one can be used.
【００６７】具体的には、図６の処理例にしたがって、
無電解めっきで銅膜を付け、電気めっきで銅膜を形成
し、プリント配線板を得た。湿式粗化が不要であり、選
択エッチング用のレジストマクス形成も不要である。レ
ジスト塗布、露光、現像が省略できる。 −実施例１３− 実施例１３では、図２２にみるように、基材１の表面の
膜形成用域（回路パターンに相当）のみに紫外レーザを
照射し、基材表面の膜形成用域のみを粗化し、無電解め
っき用の核（Ｐｄ等）付けを全面に行い、無電解めっき
および電気めっきを全面に行った後、レジスト塗布、露
光、現像によりレジストマスクを形成したあと、選択的
エッチングを行うことにより、所定パターンの導電膜２
を有するプリント配線板を得る。Specifically, according to the processing example of FIG.
A copper film was attached by electroless plating and a copper film was formed by electroplating to obtain a printed wiring board. Wet roughening is not necessary, and resist mask formation for selective etching is also unnecessary. The resist coating, exposure and development can be omitted. -Example 13-In Example 13, as shown in FIG. 22, only the film forming area (corresponding to a circuit pattern) on the surface of the base material 1 was irradiated with the ultraviolet laser, and only the film forming area on the base material surface was irradiated. Is roughened, a core (Pd etc.) for electroless plating is applied to the entire surface, electroless plating and electroplating are applied to the entire surface, and then a resist mask is formed by resist application, exposure and development, and then selective etching Conducting the conductive film 2 having a predetermined pattern
To obtain a printed wiring board.
【００６８】基材は、液晶ポリマー、ポリイミド、エポ
キシ等の樹脂基材あるいはアルミナ等のセラミック基材
など、これまでに例示したものが使えるし、粗化に関し
ても、前述の膜形成用域のみの粗化のいずれのものでも
利用可能である。具体的には、図５の処理例にしたがっ
て、無電解めっきで銅膜を付け、電気めっきで銅膜を形
成し、プリント配線板を得た。As the base material, those exemplified above, such as a liquid crystal polymer, a resin base material such as polyimide and epoxy, or a ceramic base material such as alumina, can be used, and regarding roughening, only the above-mentioned film forming area is used. Any roughening can be used. Specifically, according to the treatment example of FIG. 5, a copper film was attached by electroless plating and a copper film was formed by electroplating to obtain a printed wiring board.
【００６９】湿式粗化が不要であり、選択エッチングの
際、除去部分では粗化がなされていないため容易に除去
でき、サイドエッチを防止しつつ絶縁不良の原因となる
不要金属の残留を防止できる。 −実施例１４− 実施例１４では、基材１の表面の膜形成用域（回路パタ
ーンに相当）のみに紫外レーザを照射して基材表面の膜
形成用域のみを粗化し、その後、図２３にみるように、
基材１を、チャンバ内に入れ、基材１の表面に対しウイ
ンドウより光を照射しつつレーザＣＶＤ（熱ＣＶＤ）に
よる膜の形成を行っている。レーザＣＶＤは、反応性ガ
スの導入と同反応性ガスに対するレーザの照射を行い膜
形成する方法である。反応性ガスとしては、Ａｌ（Ｃ
Ｈ）3 、Ｃｕ（ＨＣＯＯ）2 ・２Ｈ 2 Ｏ、Ｃｕヘキサフ
ルオロアセチルアセトネート、Ｎｉ（ＣＯ）4 等が挙げ
られる。照射する光は、Ａｒレーザ、ＹＡＧレーザ、Ｃ
Ｏ2 レーザ等のいわゆる熱レーザが例示される。この光
の照射は粗化面のみに行う。Since wet roughening is not necessary, selective etching
At this time, it is easy to remove because the removed part is not roughened
Can prevent side etching and cause insulation failure.
It is possible to prevent unnecessary metal from remaining. -Example 14-In Example 14, a film forming area (circuit pattern) on the surface of the substrate 1 was formed.
Film) on the substrate surface by irradiating only the
Roughening only the formation area, and then, as shown in FIG.
The base material 1 is placed in the chamber and the surface of the base material 1 is wiped.
Laser CVD (thermal CVD) while irradiating light from the window
The film is formed by Laser CVD is a reactive gas
Of the film and the laser irradiation of the same reactive gas.
It is a method of forming. As the reactive gas, Al (C
H)3, Cu (HCOO)2・ 2H 2O, Cu hexaf
Luoroacetylacetonate, Ni (CO)FourEtc.
To be The irradiation light is Ar laser, YAG laser, C
O2A so-called thermal laser such as a laser is exemplified. This light
Is irradiated only on the roughened surface.
【００７０】粗化面の凸部で熱集中が起こり、反応性ガ
スが粗化面で分解し所定パターンの膜形成が行える。基
材は、液晶ポリマー、ポリイミド、エポキシ等の樹脂基
材あるいはアルミナ等のセラミック基材など、これまで
に例示したものが使えるし、粗化に関しても、前述の膜
形成用域のみの粗化のいずれのものでも利用可能であ
る。Heat is concentrated on the convex portions of the roughened surface, and the reactive gas is decomposed on the roughened surface to form a film having a predetermined pattern. As the base material, liquid crystal polymer, resin base material such as polyimide or epoxy, or ceramic base material such as alumina can be used, and the roughening can be performed only in the film forming area described above. Either one can be used.
【００７１】具体的には、図７の処理例にしたがって、
ＣＶＤで銅膜を付け、電気めっきで銅膜を形成し、プリ
ント配線板を得た。湿式粗化が不要であり、選択エッチ
ング用のレジストマクス形成も不要である。レジスト塗
布、露光、現像が省略できる。Specifically, according to the processing example of FIG.
A copper film was attached by CVD and a copper film was formed by electroplating to obtain a printed wiring board. Wet roughening is not necessary, and resist mask formation for selective etching is also unnecessary. The resist coating, exposure and development can be omitted.
【００７２】[0072]
【発明の効果】この発明のパターン膜形成方法では、基
材表面の粗化を紫外レーザ照射により行うため、湿式粗
化を用いずとも、凹みの深い粗化が実現でき、粗化面に
形成される膜は密着力の十分なものとなる。粗化された
基材表面を光照射により加熱すると、粗化面の凸部の先
端のみが太くアンカー効果が備わり、膜と基材の混在域
が出来るため膜の密着力はより十分なものとなる。According to the method of forming a patterned film of the present invention, since the surface of the substrate is roughened by ultraviolet laser irradiation, deep roughening can be realized without using wet roughening, and the roughened surface is formed. The resulting film has sufficient adhesion. When the surface of the roughened substrate is heated by irradiation with light, only the tips of the protrusions on the roughened surface are thick and an anchor effect is provided, and because the mixed area of the film and the substrate is created, the adhesive force of the film is more sufficient. Become.
【００７３】紫外レーザの照射を特定域に選択的に行う
場合は、特定域以外の領域に膜が残ったり、特定域に残
る膜にサイドエッチを起こさずに、特定域への膜形成が
容易に行える。基材表面に対する紫外レーザを、レーザ
ＣＶＤの反応ガスへの照射レーザとしても用い、基材表
面に対し粗化と同時にレーザＣＶＤによる膜形成を行う
と、粗化と膜形成が同時に行える利点がある。When the irradiation of the ultraviolet laser is selectively performed in the specific region, the film can be easily formed in the specific region without leaving the film in the region other than the specific region or causing the side etching in the film remaining in the specific region. You can do it. When the ultraviolet laser for the surface of the substrate is also used as a laser for irradiating the reaction gas of laser CVD and the film is formed on the surface of the substrate by laser CVD at the same time as roughening, there is an advantage that the roughening and the film formation can be performed at the same time. .
【００７４】紫外レーザの照射によっても除去されにく
い粒子が表面部分に分散されている樹脂基材を用いる
と、粒子の大きさや混合量の調節により深い凹みのある
粗化ができる。紫外レーザの照射により除去され易い粒
子が表面部分に分散されている樹脂基材を用いると、粒
子の大きさや混合量の調節により深い凹みの粗化ができ
る。When a resin base material in which particles that are difficult to be removed by irradiation with an ultraviolet laser are dispersed in the surface portion, roughening with deep dents can be achieved by adjusting the size and mixing amount of the particles. By using a resin base material in which particles that are easily removed by irradiation with an ultraviolet laser are dispersed in the surface portion, it is possible to roughen deep dents by adjusting the size and mixing amount of the particles.
【００７５】紫外レーザの照射によっても除去されにく
い粒子と紫外レーザの照射により除去され易い粒子の両
方の粒子が表面部分に分散されている樹脂基材を用いる
と、やはり、粒子の大きさや混合量の調節により深い凹
みのある粗化ができる。表面部分の一部を紫外レーザの
照射により粗化されやすい樹脂材料で形成した樹脂基材
を用いると、他の部分が紫外レーザでも粗化され難い樹
脂材料で出来ている樹脂基材であっても、基材表面の必
要部分の選択的粗化が可能となる。If a resin base material in which both the particles that are difficult to be removed by the irradiation of the ultraviolet laser and the particles that are easily removed by the irradiation of the ultraviolet laser are dispersed on the surface portion, the size and the mixing amount of the particles are also used. By adjusting the, roughening with deep dents can be made. If a resin base material is used, in which a part of the surface part is made of a resin material that is easily roughened by irradiation with an ultraviolet laser, a resin base material that is made of a resin material that is hard to be roughened by an ultraviolet laser in the other part Also, it becomes possible to selectively roughen the required portion of the substrate surface.
【００７６】膜形成物質と結合し易い物質を表面部分に
含有する樹脂基材を用いると、膜の密着力がより高ま
る。表面に金属材料を分散付着させた樹脂基材を用いる
と、深い凹みが分散現出し十分な深さの粗化が出来る。
この発明の表面粗化方法により基材表面の特定域が選択
的に粗化された基材を用いる場合、特定域以外の領域が
粗化されていないため、特定域への選択的な膜形成や、
膜形成用域以外の領域上の膜の除去が容易に行え、特定
域だけへサイドエッチのない膜を設けることが容易に行
える。When a resin base material containing a substance that easily binds to the film-forming substance on the surface portion is used, the adhesive force of the film is further enhanced. If a resin base material having a metal material dispersed and adhered on the surface is used, deep dents are dispersed and exposed, and a sufficient depth of roughening can be achieved.
When a substrate in which a specific region on the surface of the substrate is selectively roughened by the surface roughening method of the present invention is used, a region other than the specific region is not roughened, and thus a film is selectively formed on the specific region. Or
The film on the region other than the film forming region can be easily removed, and the film without side etching can be easily provided only on the specific region.
【００７７】加えて、膜形成を、反応性ガスの導入と同
反応性ガスに対する光照射を伴うＣＶＤにより行うと同
時に光照射により基材表面の粗化面の加熱をも行う場合
は、膜の密着力はより十分なものとなる。In addition, when the film formation is performed by the CVD with the introduction of the reactive gas and the irradiation of the reactive gas with the light, the roughened surface of the substrate surface is also heated by the light irradiation. Adhesion will be more sufficient.
【図１】この発明での紫外レーザの照射形態を示す概略
説明図。FIG. 1 is a schematic explanatory view showing an irradiation form of an ultraviolet laser according to the present invention.
【図２】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 2 is a process explanatory view showing a processing example of a method for processing the surface of a base material according to the present invention.
【図３】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 3 is a process explanatory view showing a processing example of a method for processing the surface of a base material according to the present invention.
【図４】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 4 is a process explanatory view showing a treatment example of a treatment method for a substrate surface according to the present invention.
【図５】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 5 is a process explanatory view showing a processing example of a method for processing the surface of a base material according to the present invention.
【図６】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 6 is a process explanatory view showing a processing example of a method for processing the surface of a base material according to the present invention.
【図７】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 7 is a process explanatory view showing a processing example of a method for processing the surface of a base material according to the present invention.
【図８】実施例１での基材表面の処理の様子を示す概略
説明図。FIG. 8 is a schematic explanatory diagram showing how the surface of the base material is treated in Example 1.
【図９】実施例２での基材表面の参考にする処理の様子
を示す概略説明図。FIG. 9 is a schematic explanatory view showing a state of a process of referring to a surface of a base material in Example 2.
【図１０】実施例２での基材表面の処理の様子を示す概
略説明図。FIG. 10 is a schematic explanatory view showing how the substrate surface is treated in Example 2.
【図１１】実施例３での基材表面の処理の様子を示す概
略説明図。FIG. 11 is a schematic explanatory diagram showing how the surface of the base material is treated in Example 3.
【図１２】実施例４での基材表面の処理の様子を示す概
略説明図。FIG. 12 is a schematic explanatory diagram showing how the surface of the base material is treated in Example 4.
【図１３】実施例５での基材表面の処理の様子を示す概
略説明図。FIG. 13 is a schematic explanatory view showing how the substrate surface is treated in Example 5.
【図１４】実施例６での基材と基材表面の処理の様子を
示す概略説明図。FIG. 14 is a schematic explanatory diagram showing how the substrate and the surface of the substrate are treated in Example 6.
【図１５】実施例７での基材と基材表面の処理の様子を
示す概略説明図。FIG. 15 is a schematic explanatory diagram showing how a substrate and a substrate surface are treated in Example 7.
【図１６】実施例８での基材と基材表面の処理の様子を
示す概略説明図。FIG. 16 is a schematic explanatory diagram showing how a substrate and a substrate surface are treated in Example 8.
【図１７】実施例９での基材と基材表面の処理の様子を
示す概略説明図。FIG. 17 is a schematic explanatory diagram showing how a substrate and a substrate surface are treated in Example 9.
【図１８】実施例９での基材作製の様子を示す概略説明
図。FIG. 18 is a schematic explanatory view showing how the base material is manufactured in Example 9.
【図１９】実施例１０での基材と基材表面の処理の様子
を示す概略説明図。FIG. 19 is a schematic explanatory diagram showing how a substrate and a substrate surface are treated in Example 10.
【図２０】実施例１１での基材と基材表面の処理の様子
を示す概略説明図。FIG. 20 is a schematic explanatory diagram showing how a substrate and a substrate surface are treated in Example 11.
【図２１】実施例１２での基材表面の処理の様子を示す
概略説明図。FIG. 21 is a schematic explanatory diagram showing how the surface of the base material is treated in Example 12.
【図２２】実施例１３での基材表面の処理の様子を示す
概略説明図。FIG. 22 is a schematic explanatory view showing how the substrate surface is processed in Example 13.
【図２３】実施例１４での基材表面の処理の様子を示す
概略説明図。FIG. 23 is a schematic explanatory diagram showing how the surface of the substrate is treated in Example 14.
【図２４】従来の基材表面の処理の様子を示す概略説明
図。FIG. 24 is a schematic explanatory view showing a state of conventional treatment of the surface of a base material.
１ 基材 ２ 所定パターンの導電膜 ３ 金属膜 1 Base Material 2 Conductive Film with Predetermined Pattern 3 Metal Film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内野々良幸 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 中嶋 勲二 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 鈴木 俊之 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 北村 啓明 大阪府門真市大字門真1048番地松下電工株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiyuki Uchinono, 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Keiji Nakajima, 1048, Kadoma, Kadoma, Osaka Prefecture (72) Inventor Toshiyuki Suzuki, 1048, Kadoma, Kadoma, Osaka Prefecture, Matsushita Electric Works Co., Ltd. (72) Hiroaki Kitamura, 1048, Kadoma, Kadoma City, Osaka, Matsushita Electric Works, Ltd.
Claims (14)
材表面の粗化を行う工程を含む基材表面の処理方法。1. A method of treating a substrate surface, which comprises the step of irradiating the substrate surface with an ultraviolet laser to roughen the substrate surface.
材表面の粗化を行う工程と粗化された基材表面に膜を形
成する工程を含む基材表面の処理方法。2. A method for treating a substrate surface, which comprises the steps of irradiating the substrate surface with an ultraviolet laser to roughen the substrate surface and forming a film on the roughened substrate surface.
する請求項１または２記載の基材表面の処理方法。3. The method for treating a substrate surface according to claim 1, wherein the roughened substrate surface is heated by light irradiation.
けに行う請求項１から３までのいずれかに記載の基材表
面の処理方法。4. The method for treating a surface of a substrate according to claim 1, wherein the irradiation of the ultraviolet laser is performed only on a specific region of the surface of the substrate.
スの導入と同反応ガスへのレーザ照射を伴うレーザＣＶ
Ｄの前記反応ガスへのレーザ照射として用い、基材表面
に対し粗化と同時に膜の形成を行う請求項２から４まで
のいずれかに記載の基材表面の処理方法。5. A laser CV in which the ultraviolet laser irradiation to the surface of the base material is accompanied by the introduction of the reaction gas and the laser irradiation to the reaction gas.
5. The method for treating a surface of a substrate according to claim 2, wherein the reaction gas of D is used for laser irradiation to roughen the surface of the substrate and simultaneously form a film.
も除去されにくい粒子が表面部分に分散されている樹脂
基材を用いる請求項１から５までのいずれかに記載の基
材表面の処理方法。6. The method for treating the surface of a base material according to claim 1, wherein a resin base material in which particles which are difficult to be removed even by irradiation with an ultraviolet laser are dispersed in the surface portion is used as the base material. .
去され易い粒子が表面部分に分散されている樹脂基材を
用いる請求項１から５までのいずれかに記載の基材表面
の処理方法。7. The method for treating the surface of a base material according to claim 1, wherein a resin base material in which particles that are easily removed by irradiation with an ultraviolet laser are dispersed in the surface portion is used as the base material.
も除去され難い粒子と紫外レーザの照射により除去され
易い粒子の両方が表面部分に分散されている樹脂基材を
用いる請求項１から５までのいずれかに記載の基材表面
の処理方法。8. A resin base material in which, as the base material, both particles that are difficult to be removed by irradiation with an ultraviolet laser and particles that are easily removed by irradiation with an ultraviolet laser are dispersed on the surface portion. The method for treating the surface of a substrate according to any one of 1.
の照射により粗化されやすい樹脂材料で形成した樹脂基
材を用いる請求項１から５までのいずれかに記載の基材
表面の処理方法。9. The treatment of the surface of the substrate according to claim 1, wherein the substrate is a resin substrate whose surface is partially formed of a resin material that is easily roughened by irradiation with an ultraviolet laser. Method.
付着させた樹脂基材を用いる請求項１から５までのいず
れかに記載の基材表面の処理方法。10. The method for treating the surface of a base material according to claim 1, wherein a resin base material in which a metal material is dispersed and attached to a surface portion is used as the base material.
合し易い物質が含まれている樹脂基材を用いる請求項２
から１０までのいずれかに記載の基材表面の処理方法。11. A resin base material having a surface portion containing a substance which easily binds to a film-forming substance, as the base material.
11. The method for treating a substrate surface according to any one of 1 to 10.
に行う請求項２から１１までのいずれかに記載の基材表
面の処理方法。12. The method for treating a surface of a base material according to claim 2, wherein the film is selectively formed on a specific region of the surface of the base material.
基材表面の特定域以外の膜だけを除去する請求項２から
１１までのいずれかに記載の基材表面の処理方法。13. After forming a film on the entire surface of the substrate,
The method for treating a surface of a base material according to claim 2, wherein only a film other than a specific region on the surface of the base material is removed.
ガスへの光照射を伴うＣＶＤにより行うとともに、前記
光照射により基材表面の粗化面の加熱をも行う請求項２
から１３までのいずれかに記載の基材表面の処理方法。14. The film formation is performed by CVD with introduction of a reactive gas and light irradiation to the reaction gas, and heating of the roughened surface of the base material is also performed by the light irradiation.
The method for treating the surface of a base material according to any one of 1 to 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26759093A JP3222660B2 (en) | 1993-10-26 | 1993-10-26 | Substrate surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26759093A JP3222660B2 (en) | 1993-10-26 | 1993-10-26 | Substrate surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07116870A true JPH07116870A (en) | 1995-05-09 |
| JP3222660B2 JP3222660B2 (en) | 2001-10-29 |
Family
ID=17446873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26759093A Expired - Fee Related JP3222660B2 (en) | 1993-10-26 | 1993-10-26 | Substrate surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3222660B2 (en) |
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