JP5820160B2 - Plating film forming method for bag-like micropipe - Google Patents
Plating film forming method for bag-like micropipe Download PDFInfo
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Description
本発明は、メッキ膜形成技術に関し、より具体的には、微小な内空間を有する袋状の微細管の内外壁面に均一な厚みのメッキ膜を形成するための方法及びシステムに関する。 The present invention relates to a plating film forming technique, and more specifically, to a method and system for forming a plating film having a uniform thickness on the inner and outer wall surfaces of a bag-like microtube having a minute inner space.
近年、情報関連機器の小型化、高機能化により、これらの機器に用いられる部品や関連機器等も微小化が要求されている。このような要求を満たすべき部品や関連機器の一つに、半導体集積回路検査機器のテストヘッドの心臓部であるコンタクトプローブがある。コンタクトプローブは、通常、例えば特許文献１の図３に記載されているように、一端が閉塞された導電チューブとプランジャとを備える。プランジャは、導電チューブの内壁面に沿って摺動し、導電チューブに対して相対移動することにより、その一端が導電チューブの他端の開口から突出するように構成されている。プランジャは、導電チューブ内に設置されたスプリングによって付勢されている。プランジャの先端が被検体に当接した際におけるプランジャと被検体との間の電気的導通により、被検体の電気回路の断線、ショート等の点検が行われることになる。 In recent years, miniaturization of parts and related devices used in these devices has been required due to downsizing and higher functionality of information related devices. One of the parts and related devices that should meet such requirements is a contact probe that is the heart of a test head of a semiconductor integrated circuit inspection device. The contact probe normally includes a conductive tube and a plunger that are closed at one end, as described in FIG. The plunger slides along the inner wall surface of the conductive tube and moves relative to the conductive tube so that one end of the plunger protrudes from the opening at the other end of the conductive tube. The plunger is biased by a spring installed in the conductive tube. Due to the electrical continuity between the plunger and the subject when the tip of the plunger comes into contact with the subject, inspection such as disconnection or short circuit of the electrical circuit of the subject is performed.
上述のように、コンタクトプローブにおいては、導電チューブとプランジャとの間の電気的導通は、導電チューブの内壁とプランジャの外壁とが接触することによって得られる。この接触の際の電気抵抗を小さくするとともに、耐摩耗性、耐食性、密着性を向上させる目的で、一般に、導電チューブの内壁とプランジャの外壁とに導電性薄膜、いわゆるメッキ膜が形成される。メッキ膜の形成は、一般に、電解メッキ又は無電解メッキのいずれを用いて行ってもよい。 As described above, in the contact probe, electrical conduction between the conductive tube and the plunger is obtained by the contact between the inner wall of the conductive tube and the outer wall of the plunger. In order to reduce the electrical resistance at the time of this contact and improve wear resistance, corrosion resistance, and adhesion, generally, a conductive thin film, so-called plated film, is formed on the inner wall of the conductive tube and the outer wall of the plunger. In general, the plating film may be formed using either electrolytic plating or electroless plating.
導電チューブのような「細管」は、その内径が長さに対して極めて小さいのが一般的である。こういった細管の内壁面にメッキ膜を形成する際の問題は、メッキ膜の形成工程に必要な各種の処理液が、液の表面張力のために細管の内部に入らないことである。液が細管の内部に入らないと、メッキ膜の形成工程において必要な脱脂液、エッチング液、活性化液、メッキ液などが細管の奥まで届かず、必要なメッキ膜を内壁面に形成することができない。こうした問題を解決する手段として、例えば特許文献１の従来技術に記載された技術が提案されている。特許文献１に記載の技術では、例えば内径４００μｍ、長さ２５００μｍの細管の内壁面にメッキ膜を形成することを目的として、細管の閉塞端側に細管の内部と外部とを連通する貫通孔が設けられる。この貫通孔の存在によって、細管内の閉塞端側までメッキ液などを侵入させることができるようになるため、内壁面へのメッキ膜の形成が可能になる。 In general, a “narrow tube” such as a conductive tube has an inner diameter that is extremely small with respect to its length. A problem in forming a plating film on the inner wall surface of such a thin tube is that various processing liquids necessary for the plating film forming process do not enter the thin tube due to the surface tension of the liquid. If the liquid does not enter the inside of the narrow tube, the necessary degreasing solution, etching solution, activation solution, plating solution, etc. in the plating film formation process will not reach the back of the narrow tube, and the necessary plating film should be formed on the inner wall surface. I can't. As means for solving such a problem, for example, a technique described in the prior art of Patent Document 1 has been proposed. In the technique described in Patent Document 1, for example, for the purpose of forming a plating film on the inner wall surface of a narrow tube having an inner diameter of 400 μm and a length of 2500 μm, a through hole that connects the inside and the outside of the narrow tube is provided on the closed end side of the thin tube. Provided. Due to the presence of the through hole, it becomes possible to allow the plating solution or the like to penetrate to the closed end side in the narrow tube, so that a plating film can be formed on the inner wall surface.
特許文献２には、両端が開放された細管の内壁面へのメッキ膜形成に関する技術が提案されている。この技術では、細管の内側と外側に存在するそれぞれのメッキ液の濃度を、細管の内側のメッキ液を強制的に流動させて同等に保つことによって、正常で均一なメッキ膜を内壁面に形成するものである。 Patent Document 2 proposes a technique related to the formation of a plating film on the inner wall surface of a narrow tube whose both ends are open. This technology forms a normal and uniform plating film on the inner wall surface by forcibly flowing the plating solution inside the narrow tube and keeping the concentration equal to each other. To do.
これらの技術のように、内径が小さく長さが長い細管であっても、閉塞端に貫通孔を設けることができるか又は両端が開放されている場合には、メッキ膜形成に必要な各種の処理液が細管の内部の奥にまで到達できるため、内壁面へのメッキ膜の形成が可能となる。 Like these techniques, even if the inner diameter is small and the length is long, the closed end can be provided with a through-hole, or if both ends are open, various types of plating film formation required Since the processing liquid can reach the inside of the narrow tube, it is possible to form a plating film on the inner wall surface.
上述のように、細管の内壁面にメッキ膜を形成する従来の技術では、両端が開放されている細管や、袋状であっても閉塞端側に貫通孔を設けることができる細管の場合には、内壁面へのメッキは不可能ではない。しかしながら、内径（より具体的には、細管の開放端の内径）が例えば約３００μｍより小さく長さが長い細管のような極めて微小な内空間を有する袋状の細管（以下、本明細書においては「袋状微細管」という。）の場合には、袋状微細管の閉塞端の内外をつなぐ貫通孔を設けること自体が極めて難しく、特に内径が約１００μｍより小さい袋状微細管においては、貫通孔を設けることは技術的にほぼ不可能である。 As described above, in the conventional technique of forming a plating film on the inner wall surface of a thin tube, in the case of a thin tube that is open at both ends, or a thin tube that can be provided with a through hole on the closed end side even in a bag shape. The plating on the inner wall is not impossible. However, the inner diameter (more specifically, the inner diameter of the open end of the thin tube) is a bag-like thin tube having a very small inner space such as a thin tube having a length smaller than about 300 μm (for example, in the present specification, hereinafter). In the case of “bag-like microtube”), it is extremely difficult to provide a through-hole that connects the inside and outside of the closed end of the bag-like microtube. It is technically impossible to provide a hole.
また、たとえ貫通孔を設けて内壁面をメッキする技術を用いることができるような内径を有する袋状の細管の場合であっても、貫通孔から袋状の細管の内部に塵埃などが侵入して内壁面に付着し、袋状の細管の接触抵抗が増大し、動作不良が発生するおそれがある。特許文献１では、こうした問題に対応するための方法として、細管内の閉塞端とスプリングの端部との間に閉塞部材を設けることによって、貫通孔による導電チューブの内部と外部との連通を遮断する方法が提案されている。しかしながら、こうした方法は、細管の内部にさらに小径の部品を挿入し、所望の位置に位置決めするという極めて複雑な工程を必要とするため、実際の製品への適用は難しいと考えられる。 Even in the case of a bag-like tubule having an inner diameter that allows the use of a technique for plating the inner wall surface by providing a through-hole, dust or the like enters the bag-like tubule from the through-hole. May adhere to the inner wall surface, increase the contact resistance of the bag-like tubule, and cause malfunction. In Patent Document 1, as a method for coping with such a problem, by providing a blocking member between the closed end in the narrow tube and the end of the spring, communication between the inside and outside of the conductive tube by the through hole is blocked. A method has been proposed. However, such a method requires a very complicated process of inserting a smaller-diameter part into the inside of the narrow tube and positioning it at a desired position, so that it is considered difficult to apply to an actual product.
さらに、袋状の細管においては、貫通孔を設けることができる場合であっても、内部におけるメッキ液の拡散が不均一となり、袋状の細管の入り口近くの内壁面と奥の内壁面とでメッキ膜厚に差が生じるため、均一なメッキ膜の形成は不可能であった。 Furthermore, even in the case where the through-holes can be provided in the bag-like tubule, the diffusion of the plating solution inside becomes uneven, and the inner wall surface near the entrance of the bag-like tubule and the inner wall surface in the back Due to the difference in plating film thickness, it was impossible to form a uniform plating film.
本発明は、内径が極めて小さく長さが長い袋状の細管、中でも内径が約１００μｍ以下のアスペクト比の大きい袋状微細管の内壁面に対しても、貫通孔を設けることなく均一なメッキ膜を形成することが可能な方法及びシステムを提供することを目的とする。 The present invention provides a uniform plated film without providing a through-hole on the inner wall surface of a bag-like tubule having an extremely small inner diameter and a long length, in particular, a bag-like fine tube having an inner diameter of about 100 μm or less and a large aspect ratio. It is an object to provide a method and system capable of forming
本発明者らは、内径が約１００μｍ以下の微小な内空間を有する袋状微細管であっても、プラズマ処理による内壁面の濡れ性の向上と内空間への処理液の新たな注入方法とを組み合わせることによって、通常の方法では処理液が入らない微小な空間にも処理液を注入できることを見出し、本発明を完成させた。 The present inventors have improved the wettability of the inner wall surface by plasma treatment and a new method for injecting a treatment liquid into the inner space even with a bag-like microtube having an inner diameter of about 100 μm or less. By combining the above, it has been found that the treatment liquid can be injected into a minute space where the treatment liquid does not enter by a normal method, and the present invention has been completed.
本発明の第１の態様は、一端が閉じた袋状微細管の外壁と内空間の内壁とにメッキ膜を形成する方法を提供する。本方法は、真空雰囲気内に配置された袋状微細管にプラズマを照射することにより、袋状微細管の内壁及び外壁の表面の不純物を除去するプラズマ洗浄工程と、不純物が除去され内空間に空気が残留していない状態の真空雰囲気内の袋状微細管を脱脂液に浸漬させ、真空雰囲気を大気圧雰囲気に置換することにより、袋状微細管の内空間の全体に脱脂液を注入し、袋状微細管の内壁及び外壁の脱脂処理を行う脱脂工程とを含む。本方法は、さらに、脱脂された袋状微細管の少なくとも内空間に空気が入らないようにしながら脱脂液を洗浄液に置換し、袋状微細管を洗浄する脱脂液洗浄工程と、洗浄された袋状微細管の少なくとも内空間に空気が入らないようにしながら洗浄液をメッキ液に置換し、袋状微細管にパルスリバース電気メッキ処理を行うメッキ工程と、を含むことを特徴とする。 The first aspect of the present invention provides a method of forming a plating film on the outer wall of the bag-like microtube closed at one end and the inner wall of the inner space. The method includes a plasma cleaning step of removing impurities on the inner and outer walls of the bag-like microtube by irradiating the bag-like microtube arranged in a vacuum atmosphere with plasma, and removing the impurities into the inner space. By immersing the bag-like micropipe in a vacuum atmosphere with no air remaining in the degreasing liquid and replacing the vacuum atmosphere with an atmospheric pressure atmosphere, the degreasing liquid is injected into the entire inner space of the bag-like micropipe. And a degreasing step of degreasing the inner wall and the outer wall of the bag-like micropipe. The method further includes a degreasing liquid cleaning step of cleaning the bag-shaped microtube by replacing the degreasing liquid with a cleaning liquid while preventing air from entering at least the inner space of the degreased bag-shaped microtubule, and the cleaned bag And a plating step in which the cleaning liquid is replaced with a plating solution so that air does not enter at least the inner space of the fine tube, and the bag-like fine tube is subjected to a pulse reverse electroplating process.
一実施形態においては、本方法は、さらに、上述のメッキ工程の後、メッキされた袋状微細管の少なくとも内空間に空気が入らないようにしながら袋状微細管を洗浄液で洗浄し、洗浄後に袋状微細管を乾燥させる工程を含むことが好ましい。本方法は、さらに、乾燥された袋状微細管を真空雰囲気内に配置した後、内空間に空気が残留していない状態の袋状微細管をメッキ液とは別のメッキ液に浸漬させ、真空雰囲気を大気圧雰囲気に置換することにより、袋状微細管の内空間の全体に別のメッキ液を注入し、袋状微細管に別のメッキ液によるパルスリバース電気メッキ処理を行う工程を含むことが好ましい。 In one embodiment, the method further includes, after the above-described plating step, washing the bag-like microtubule with a cleaning liquid while preventing air from entering at least the inner space of the plated bag-like microtubule, and after washing, It is preferable to include a step of drying the bag-shaped microtubule. In the present method, after the dried bag-like microtube is placed in a vacuum atmosphere, the bag-like microtube in a state where no air remains in the inner space is immersed in a plating solution different from the plating solution, It includes a step of injecting another plating solution into the entire inner space of the bag-like micropipe by replacing the vacuum atmosphere with an atmospheric pressure atmosphere, and subjecting the bag-like micropipe to pulse reverse electroplating with another plating solution. It is preferable.
一実施形態においては、本方法は、さらに、脱脂液洗浄工程の後、洗浄された袋状微細管の少なくとも内空間に空気が入らないようにしながら洗浄液をエッチング液に置換してエッチング処理を行うエッチング工程と、エッチングされた袋状微細管の少なくとも内空間に空気が入らないようにしながらエッチング液を洗浄液に置換して袋状微細管を洗浄するエッチング液洗浄工程とを含むことが好ましい。エッチング工程を行った場合には、本方法は、さらに、エッチング工程に続く袋状微細管の洗浄工程の後、洗浄された袋状微細管の少なくとも内空間に空気が入らないようにしながら洗浄液を活性化液に置換して活性化処理を行う活性化工程と、活性化された袋状微細管の少なくとも内空間に空気が入らないようにしながら活性化液を洗浄液に置換して袋状微細管を洗浄する活性化液洗浄工程とを含むことが好ましい。 In one embodiment, the method further performs an etching process after the degreasing liquid cleaning step by replacing the cleaning liquid with an etching liquid while preventing air from entering at least the inner space of the cleaned bag-like micropipe. It is preferable to include an etching step and an etching solution cleaning step of cleaning the bag-shaped microtube by replacing the etching solution with a cleaning solution while preventing air from entering at least the inner space of the etched bag-shaped microtube. In the case where the etching process is performed, the method further includes the step of cleaning the bag-shaped microtubules after the etching process with a cleaning solution while preventing air from entering at least the inner space of the cleaned bag-shaped microtubules. An activation process in which the activation process is performed by substituting the activation liquid, and the bag-shaped microtubule is obtained by replacing the activation liquid with the cleaning liquid while preventing air from entering at least the inner space of the activated bag-shaped microtubule. It is preferable to include an activation liquid cleaning step for cleaning the liquid.
本発明の第２の態様によれば、本発明は、一端が閉じた袋状微細管の内空間の全体に液体を注入するための液体注入装置を提供する。本装置は、真空チャンバと、真空チャンバの内部に配置され、袋状微細管と液体とを収容可能な容器と、真空チャンバの内部の空気を真空チャンバの外部に排出するためのポンプと、真空チャンバの内部と外部とを連通する排出口とを含む排気手段と、真空チャンバの内部に配置された容器の内部と真空チャンバの外部とを連通する流路と、流路内の液体の通過又は遮断を制御するためのバルブとを含む液体導入手段と、真空チャンバの外部に配置され、流路を介して容器の内部に供給される液体を収容可能な液体容器と、真空チャンバの内部の真空雰囲気を大気圧雰囲気に置換するための大気導入手段と、を備えることを特徴とする。 According to a second aspect of the present invention, the present invention provides a liquid injection device for injecting liquid into the entire inner space of a bag-like microtube whose one end is closed. The apparatus includes a vacuum chamber, a container that is disposed inside the vacuum chamber and can store a bag-like microtube and a liquid, a pump for discharging the air inside the vacuum chamber to the outside of the vacuum chamber, a vacuum An exhaust means including a discharge port that communicates the inside and the outside of the chamber, a channel that communicates the inside of the container disposed inside the vacuum chamber and the outside of the vacuum chamber, and the passage of the liquid in the channel A liquid introducing means including a valve for controlling the shutoff; a liquid container disposed outside the vacuum chamber and capable of containing a liquid supplied to the inside of the container via the flow path; and a vacuum inside the vacuum chamber Air introduction means for replacing the atmosphere with an atmospheric pressure atmosphere.
本発明の第３の態様によれば、本発明は、一端が閉じた袋状微細管の外壁と内空間の内壁とにメッキ膜を形成するためのメッキ膜形成システムを提供する。本システムは、真空雰囲気の真空チャンバの内部に配置された袋状微細管に照射されるプラズマを発生させるプラズマ発生手段を備えるプラズマ洗浄装置と、請求項５に記載の液体注入装置において液体として脱脂液を用いた、プラズマの作用によって不純物が除去された袋状微細管の内空間に脱脂液を注入するための脱脂液注入装置と、少なくとも内空間に空気が入らないようにしながら洗浄液を用いて洗浄され内空間にメッキ液が入れられた袋状微細管にパルスリバース電気メッキを行うメッキ装置と、を備えることを特徴とする。 According to the third aspect of the present invention, the present invention provides a plating film forming system for forming a plating film on the outer wall of the bag-shaped microtube closed at one end and the inner wall of the inner space. The present system includes a plasma cleaning device including plasma generating means for generating plasma irradiated to a bag-like microtube disposed inside a vacuum chamber in a vacuum atmosphere, and degreasing as liquid in the liquid injection device according to claim 5. Using a degreasing liquid injection device for injecting the degreasing liquid into the inner space of the bag-like microtube from which impurities have been removed by the action of plasma, and a cleaning liquid while preventing air from entering the inner space at least And a plating apparatus for performing pulse reverse electroplating on a bag-like microtube that has been cleaned and in which a plating solution is placed.
一実施形態によれば、本システムは、請求項５に記載の液体注入装置において液体として前述のメッキ液とは別のメッキ液を用い、前述のメッキ液による電気メッキ処理が行われた袋状微細管の内空間に別のメッキ液を注入するためのメッキ液注入装置と、袋状微細管に別のメッキ液によるパルスリバース電気メッキ処理を行うメッキ装置と、を備えることが好ましい。 According to one embodiment, this system uses a plating solution different from the above-described plating solution as the liquid in the liquid injecting device according to claim 5, and the bag is subjected to electroplating with the above-described plating solution. It is preferable to include a plating solution injection device for injecting another plating solution into the inner space of the microtube, and a plating device for performing pulse reverse electroplating treatment with another plating solution on the bag-like microtube.
本発明によれば、プラズマ処理工程において袋状微細管をプラズマ洗浄することによって、袋状微細管の微小な内空間の壁面においても効果的に不純物を除去して壁面の濡れ性を向上させることができ、その後、脱脂処理工程及びその後の工程において新規な注入方法を利用して、壁面の濡れ性が向上し且つ空気が残留していない内空間全体に脱脂液及びその後の処理液を注入することができる。さらに、内空間全体にメッキ液を注入した後のパルスリバース電気メッキ処理によって、袋状微細管の壁面に均一な厚みのメッキ膜を形成することができる。 According to the present invention, the bag-like micropipe is plasma-cleaned in the plasma processing step, so that impurities can be effectively removed even on the wall surface of the minute inner space of the bag-like micropipe and the wettability of the wall is improved. Then, using a novel injection method in the degreasing process and the subsequent process, the degreasing liquid and the subsequent processing liquid are injected into the entire inner space where the wettability of the wall surface is improved and no air remains. be able to. Furthermore, a plating film having a uniform thickness can be formed on the wall surface of the bag-like microtube by pulse reverse electroplating after injecting the plating solution into the entire inner space.
以下、本発明に係る袋状微細管へのメッキ膜形成方法を詳細に示す。図１は、本発明の一実施形態に係る、袋状微細管にメッキ膜を形成するための方法のフロー図である。本発明において、メッキ膜を形成することができる袋状微細管は、径が極めて小さい中空の内空間を有する一端が閉じた形状の微細な管状部材で、断面の形状は円形であることが好ましく、その材質は、例えば真鍮、ベリリウム銅、快削黄銅といった金属とすることができる。本発明によれば、例えば内空間の径（すなわち、袋状微細管の内径）が約１００μｍ、内空間の長さ（すなわち、内空間の入り口から最奥部までの長さ）が約１４００μｍなどといったアスペクト比の大きな袋状微細管であっても、その内外壁面に均一なメッキ膜を形成することができる。袋状微細管の外壁の形状は、特に限定されるものではなく、例えば外壁のいずれかの位置にいずれかの形状の突起部が設けられた形状であっても良い。一方、袋状微細管の内空間の壁面は、突起が存在しない平坦な面であることが好ましい。 Hereinafter, a method for forming a plating film on a bag-like microtube according to the present invention will be described in detail. FIG. 1 is a flowchart of a method for forming a plating film on a bag-shaped microtubule according to an embodiment of the present invention. In the present invention, the bag-shaped microtube capable of forming a plating film is a fine tubular member having a hollow inner space with a very small diameter and closed at one end, and the cross-sectional shape is preferably circular. The material can be a metal such as brass, beryllium copper, or free-cutting brass. According to the present invention, for example, the diameter of the inner space (that is, the inner diameter of the bag-shaped microtubule) is about 100 μm, the length of the inner space (that is, the length from the entrance to the innermost portion) is about 1400 μm, etc. Even with a bag-like micropipe having a large aspect ratio, a uniform plating film can be formed on the inner and outer wall surfaces. The shape of the outer wall of the bag-like micropipe is not particularly limited, and may be a shape in which a protruding portion having any shape is provided at any position on the outer wall, for example. On the other hand, the wall surface of the inner space of the bag-like microtube is preferably a flat surface on which no protrusion exists.
以下の説明においては、本発明の一実施形態として、袋状微細管の内外壁面に２層のメッキ膜を形成する場合について説明する。ここでは、ベリリウム銅製の袋状微細管（内径が１００μｍ、内空間の入り口から最奥部までの長さが１３００μｍ）の内外壁面上に直接形成されるメッキ膜をニッケルメッキ膜とし、ニッケルメッキ膜の上にさらに形成されるメッキ膜を金メッキ膜とする。こうしたメッキ膜の構成においては、一般に、ニッケルメッキ膜は、耐食性及び硬度の向上を目的とし、金メッキ膜は、耐食性及び導電性の向上を目的としている。なお、こうしたメッキ膜の構成以外にも、例えば、密着性向上を目的として銅メッキ膜を形成し、その上にニッケルメッキ膜と金メッキ膜とを形成した構成とすることもでき、本発明に係るメッキ膜の形成方法は、こうした三層のメッキ膜構成の場合にも適用可能である。 In the following description, a case where two layers of plating films are formed on the inner and outer wall surfaces of a bag-like microtube will be described as an embodiment of the present invention. Here, the plating film directly formed on the inner and outer wall surfaces of the beryllium copper bag-like micropipe (inner diameter is 100 μm and the length from the entrance to the innermost part is 1300 μm) is a nickel plating film. A plating film further formed on the substrate is a gold plating film. In such a plating film configuration, the nickel plating film is generally intended to improve corrosion resistance and hardness, and the gold plating film is intended to improve corrosion resistance and conductivity. In addition to the configuration of the plating film, for example, a copper plating film may be formed for the purpose of improving adhesion, and a nickel plating film and a gold plating film may be formed thereon. The plating film forming method is also applicable to such a three-layer plating film configuration.
１．袋状微細管の製造
袋状微細管は、当業者に周知の方法で製造することができる。袋状微細管の製造方法の一例は、以下のとおりである。まず、所定の合金組成を満たすように複数の原料粉末を混合して原料混合粉末を調製する。この原料混合粉末から溶解法によりインゴットを作製する。次いで、線引き加工、圧延加工、鍛造加工などの方法によって、所定の直径を有する合金線材を作製する。これを必要な長さに切断した後、先端部から切削加工によって内空間を形成し、最終的に袋状微細管を製造する。
1. Production of bag-like micropipe The bag-like micropipe can be produced by a method well known to those skilled in the art. An example of the manufacturing method of a bag-like microtube is as follows. First, a raw material mixed powder is prepared by mixing a plurality of raw material powders so as to satisfy a predetermined alloy composition. An ingot is produced from this raw material mixed powder by a melting method. Next, an alloy wire having a predetermined diameter is produced by a method such as wire drawing, rolling, or forging. After cutting this to a required length, an inner space is formed by cutting from the tip, and finally a bag-like microtube is manufactured.
２．プラズマ洗浄処理工程
上述の製造工程によって製造された袋状微細管の内外壁面は、製造の際に付着した油分や切削屑などの不純物によって表面が汚れており、このままでは表面上にメッキ膜を形成することができない。従って、こうした不純物を除去するために、通常は、壁面の表面の脱脂液による脱脂処理が必要である。しかしながら、このような壁面は、通常、不純物によって表面の濡れ性が低下している。したがって、表面の濡れ性の低下と液の表面張力の影響により、袋状微細管の内空間に液が入っていかず、内空間の全体に脱脂液を注入することはきわめて難しい。この問題を解決するため、本発明においては、脱脂液による脱脂処理の前処理として、プラズマによる洗浄処理を行う。プラズマによって洗浄処理を行うことにより、袋状微細管の最奥部であっても内壁面の表面の不純物が除去されて濡れ性が向上し、内空間の奥まで脱脂液を注入することが可能になる。
2. Plasma cleaning process The inner and outer wall surfaces of the bag-like microtube manufactured by the manufacturing process described above are contaminated with impurities such as oil and cutting debris attached during the manufacturing process, and a plating film is formed on the surface as it is. Can not do it. Therefore, in order to remove such impurities, degreasing treatment with a degreasing liquid on the surface of the wall surface is usually required. However, such wall surfaces usually have reduced surface wettability due to impurities. Therefore, due to the decrease in surface wettability and the surface tension of the liquid, the liquid does not enter the inner space of the bag-like microtube, and it is extremely difficult to inject the degreasing liquid into the entire inner space. In order to solve this problem, in the present invention, as a pretreatment for the degreasing treatment using the degreasing liquid, a cleaning treatment using plasma is performed. By cleaning with plasma, impurities on the inner wall surface are removed even at the innermost part of the bag-like micropipe, improving wettability, and degreasing liquid can be injected deep into the inner space. become.
プラズマ洗浄処理工程は、本発明の一実施形態においては、市販のプラズマ処理装置（例えば、ヤマト科学株式会社のプラズマクリーナ ＰＤＣ２００）を用いて行うことができる。プラズマ洗浄処理工程は、以下のように行われる。まず、プラズマ処理装置のチャンバ内に袋状微細管が配置される。袋状微細管は、例えばガラスシャーレ等の容器に入れた状態でチャンバ内に配置されることが好ましい。次いで、プラズマ処理の条件を設定し、プラズマ洗浄処理を行う。プラズマ洗浄処理を行う際の条件は、本発明の一実施形態においては、例えば上述のプラズマ処理装置を用いる場合には、空気プラズマを用いて、真空度約１０Ｐａ、出力３００Ｗ、１分間以上という条件での処理が好ましい。プラズマ洗浄処理が完了した後、チャンバを大気圧に戻し、袋状微細管が取り出される。洗浄ガスとしては、空気、アルゴンガス、水素ガスなどを用いることができる。 In one embodiment of the present invention, the plasma cleaning process can be performed using a commercially available plasma processing apparatus (for example, a plasma cleaner PDC200 from Yamato Scientific Co., Ltd.). The plasma cleaning process is performed as follows. First, a bag-like microtube is disposed in a chamber of a plasma processing apparatus. It is preferable that the bag-like micropipe is disposed in the chamber in a state of being put in a container such as a glass petri dish. Next, plasma processing conditions are set, and plasma cleaning processing is performed. In one embodiment of the present invention, for example, in the case of using the above-described plasma processing apparatus, the conditions for performing the plasma cleaning process are such that air plasma is used, the degree of vacuum is about 10 Pa, the output is 300 W, and the time is 1 minute or more. Is preferable. After the plasma cleaning process is completed, the chamber is returned to atmospheric pressure, and the bag-like microtube is taken out. As the cleaning gas, air, argon gas, hydrogen gas, or the like can be used.
図２は、プラズマ洗浄による表面の濡れ性の向上を示す実験の結果を示す写真であり、プラズマ洗浄処理前後の試験片の表面と液体との接触角を測定した結果の写真である。実験の方法は以下のとおりである。まず、試験片Ａ、Ｂ（真鍮製、２０ｍｍ×２０ｍｍ）を、ヘプタンにオレイン酸を０．０５％含有させたものに浸漬し、乾燥させた。次いで、ガラスシャーレに試験片Ａを乗せプラズマ処理を行った。プラズマ処理の条件は、上述したとおりである。プラズマ処理を行った試験片Ａとプラズマ処理を行っていない試験片Ｂに、純水１μＬを滴下し、その水滴と試験片表面との接触角を測定、比較した。図２から、プラズマ洗浄処理を行った場合（図２Ａ）の接触角が、プラズマ洗浄処理を行わない場合（図２Ｂ）の接触角と比べて、極めて小さくなっており、表面の濡れ性が向上していることが分かる。 FIG. 2 is a photograph showing a result of an experiment showing an improvement in wettability of the surface by plasma cleaning, and is a photograph of a result of measuring a contact angle between the surface of the test piece and the liquid before and after the plasma cleaning treatment. The method of the experiment is as follows. First, test pieces A and B (made of brass, 20 mm × 20 mm) were dipped in heptane containing 0.05% oleic acid and dried. Next, the test piece A was placed on a glass petri dish and subjected to plasma treatment. The conditions for the plasma treatment are as described above. 1 μL of pure water was dropped onto the test piece A subjected to plasma treatment and the test piece B not subjected to plasma treatment, and the contact angle between the water droplet and the test piece surface was measured and compared. From FIG. 2, the contact angle when the plasma cleaning process is performed (FIG. 2A) is extremely small compared to the contact angle when the plasma cleaning process is not performed (FIG. 2B), and the surface wettability is improved. You can see that
プラズマ洗浄処理工程における処理条件について、発明者らは、種々の実験を行っている。それらの実験によれば、プラズマ洗浄処理の効果は、プラズマ処理装置において十分な出力で処理ができれば、プラズマ処理装置内における袋状微細管の位置及び開口の向きに依存しないことが分かった。図３には、開口部の向きによる洗浄効果（接触角の変化）の実験結果を示す。開口部の幅が０．５ｍｍ、内空間の奥行きが約１５ｍｍの微小空間サンプルを用いて、上述のプラズマ処理装置によって処理時間１分、出力２００Ｗ、真空度１０Ｐａの条件で処理した。微小空間サンプルは、２０ｍｍ角の真鍮板２枚の間に「コ」の字型の厚さ０．５ｍｍのシリコンシートを挟むことによって作成した。プラズマ処理装置内に、開口部の向きをそれぞれ変えて５つの微小空間サンプルを配置した。プラズマ洗浄処理後、微小空間サンプルを分解し、２枚の真鍮板のうちの１枚の微小空間に相当する部分に水滴を滴下して、接触角を測定した。接触角の測定位置は、微小空間サンプルの開口部から１０ｍｍの位置である。図３から、プラズマ洗浄処理後の接触角は、開口部の向きに依存しないことが分かる。したがって、本発明に係るプラズマ洗浄処理においては、多数の袋状微細管をその向きや配置を考慮する必要なく同時に洗浄処理することが可能であることが分かる。 The inventors have conducted various experiments on the processing conditions in the plasma cleaning process. According to these experiments, it has been found that the effect of the plasma cleaning process does not depend on the position of the bag-shaped microtubule and the direction of the opening in the plasma processing apparatus as long as the processing can be performed with a sufficient output in the plasma processing apparatus. FIG. 3 shows the experimental results of the cleaning effect (change in contact angle) depending on the orientation of the opening. Using a minute space sample with an opening width of 0.5 mm and an inner space depth of about 15 mm, the sample was processed by the above-described plasma processing apparatus under the conditions of a processing time of 1 minute, an output of 200 W, and a degree of vacuum of 10 Pa. The minute space sample was prepared by sandwiching a “U” -shaped silicon sheet having a thickness of 0.5 mm between two 20 mm square brass plates. Five microspace samples were arranged in the plasma processing apparatus while changing the direction of the opening. After the plasma cleaning treatment, the micro space sample was disassembled, and water droplets were dropped on a portion corresponding to one micro space of the two brass plates, and the contact angle was measured. The measurement position of the contact angle is a position 10 mm from the opening of the minute space sample. It can be seen from FIG. 3 that the contact angle after the plasma cleaning process does not depend on the direction of the opening. Therefore, it can be seen that in the plasma cleaning process according to the present invention, a large number of bag-like microtubes can be cleaned simultaneously without having to consider their orientation and arrangement.
３．２段階真空注入方法による脱脂液の注入
プラズマ洗浄処理工程によって壁面の不純物が除去されて濡れ性が向上した袋状微細管は、次いで、脱脂処理が行われる。脱脂処理を行うためには、内空間の全体に脱脂液が注入されなければならない。しかしながら、内壁面の濡れ性が向上したとしても、脱脂液の表面張力の影響により、内径が極めて小さい袋状微細管の内空間全体に脱脂液を注入することは難しい。そこで、本発明においては、本発明者らが考案した２段階真空注入方法を用いて、内空間に脱脂液を注入する。なお、この２段階真空注入方法は、ここでの脱脂液の注入のみに用いられるのではなく、本発明に係るメッキ膜形成方法において袋状微細管の内空間に空気が存在している場合に、内空間に処理液（例えば、金メッキ液）を注入する際のいずれにも用いることができる。
3. Degreasing liquid injection by a two-stage vacuum injection method The bag-like microtube whose wall wettability is improved by removing impurities on the wall surface by the plasma cleaning process is then degreased. In order to perform the degreasing process, the degreasing liquid must be injected into the entire inner space. However, even if the wettability of the inner wall surface is improved, it is difficult to inject the degreasing liquid into the entire inner space of the bag-like microtube having an extremely small inner diameter due to the influence of the surface tension of the degreasing liquid. Therefore, in the present invention, the degreasing liquid is injected into the inner space using the two-stage vacuum injection method devised by the present inventors. This two-stage vacuum injection method is not used only for the injection of the degreasing liquid here, but in the case where air is present in the inner space of the bag-like microtube in the plating film forming method according to the present invention. It can be used for any of the cases where a processing liquid (for example, gold plating liquid) is injected into the inner space.
図４は、本発明の一実施形態に係る、２段階真空注入方法を実現するための装置４０の概略図である。装置４０は、真空チャンバ４１と、該真空チャンバ４１内の容器４７の内部とパイプ４２を通して接続された容器４３と、容器４３内に保持された脱脂液４４と、パイプ４２の連通又は遮断を制御することができるバルブ４５と、真空チャンバ４１内と外部とを連通するパイプ及びバルブを備える大気導入手段４８と、チャンバ内４１の空気を排出する排気口４９とを備える。真空チャンバ内の容器４７内には袋状微細管４６が入れられる。脱脂液４４は、特に限定されるものではなく、電気メッキの前処理において一般に用いられる市販の脱脂液（例えば、中央化学株式会社のギルデオンＭＫ３３０）とすることができる。なお、ここでは、容器４３内に入れられるのは脱脂液であるが、液４４は、処理に応じて必要な処理液とされる。 FIG. 4 is a schematic diagram of an apparatus 40 for realizing a two-stage vacuum injection method according to an embodiment of the present invention. The apparatus 40 controls the communication or blocking of the vacuum chamber 41, the container 43 connected to the inside of the container 47 in the vacuum chamber 41 through the pipe 42, the degreasing liquid 44 held in the container 43, and the pipe 42. And an air introduction means 48 having a pipe and a valve for communicating the inside of the vacuum chamber 41 with the outside, and an exhaust port 49 for discharging the air in the chamber 41. A bag-like microtube 46 is placed in a container 47 in the vacuum chamber. The degreasing liquid 44 is not particularly limited, and may be a commercially available degreasing liquid (for example, Gildeon MK330 manufactured by Chuo Chemical Co., Ltd.) generally used in the pretreatment of electroplating. Here, it is the degreasing liquid that is put in the container 43, but the liquid 44 is a necessary processing liquid according to the processing.
本発明に係る２段階真空注入方法は、装置４０を用いて以下の手順で行われる。まず、プラズマ洗浄が終了した袋状微細管４６が容器４７に入れられ、真空チャンバ４１内に配置される。容器４３内には脱脂液４４が入れられ、容器４７の内部と容器４３の内部とが、パイプ４２を介して連通される。パイプ４２に設けられたバルブ４５が閉じられ、真空チャンバ内の空気が真空ポンプ（図示せず）によって排出口４９から排出される。真空チャンバ４１内が十分な真空雰囲気になった後（本発明の一実施形態においては、１０Ｐａ程度）、バルブ４５を開放する。このとき、真空チャンバ４１内が真空雰囲気であるため、脱脂液４４は、バルブ４５の開放に伴って容器４７内に供給される。脱脂液４４は、容器４７内において袋状微細管４６全体が脱脂液４４に浸漬するのに十分な量が供給される。容器４７内の袋状微細管４６が脱脂液４４に十分に浸漬されたことを確認した後、バルブ４８を開放し（パージする）、真空ポンプを停止する。この方法によれば、真空チャンバ４１内を真空雰囲気にすることで袋状微細管４６の内空間に滞留している空気が排出され、内空間の内壁面は濡れ性が向上しているため、容器４７内に脱脂液４４が供給されたときに脱脂液４４が袋状微細管４６の内空間に入り込む。この時点でも脱脂液４４は袋状微細管４６の内空間に注入されているが、次に真空チャンバ４１内に空気が導入されたときに、より確実に脱脂液４４が袋状微細管４６の内空間に押し込まれることになる。 The two-stage vacuum injection method according to the present invention is performed using the apparatus 40 according to the following procedure. First, the bag-like micropipe 46 after the plasma cleaning is placed in a container 47 and placed in the vacuum chamber 41. A degreasing solution 44 is placed in the container 43, and the inside of the container 47 and the inside of the container 43 are communicated with each other through a pipe 42. The valve 45 provided in the pipe 42 is closed, and the air in the vacuum chamber is discharged from the discharge port 49 by a vacuum pump (not shown). After the inside of the vacuum chamber 41 becomes a sufficient vacuum atmosphere (in one embodiment of the present invention, about 10 Pa), the valve 45 is opened. At this time, since the inside of the vacuum chamber 41 is in a vacuum atmosphere, the degreasing liquid 44 is supplied into the container 47 as the valve 45 is opened. A sufficient amount of the degreasing liquid 44 is supplied so that the entire bag-like micropipe 46 is immersed in the degreasing liquid 44 in the container 47. After confirming that the bag-like micropipe 46 in the container 47 is sufficiently immersed in the degreasing liquid 44, the valve 48 is opened (purged) and the vacuum pump is stopped. According to this method, air staying in the inner space of the bag-like micropipe 46 is discharged by making the vacuum chamber 41 a vacuum atmosphere, and the inner wall surface of the inner space has improved wettability. When the degreasing liquid 44 is supplied into the container 47, the degreasing liquid 44 enters the inner space of the bag-like microtube 46. Even at this time, the degreasing liquid 44 is injected into the inner space of the bag-like micropipe 46, but when the air is next introduced into the vacuum chamber 41, the degreasing liquid 44 is more reliably transferred to the bag-like micropipe 46. It will be pushed into the inner space.
図５は、２段階真空注入装置４０を用いて、袋状微細管の内空間に液を注入した実験の結果を示す写真である。袋状微細管の内空間の径は、２００μｍ、１００μｍ、及び５０μｍとし、内空間の長さは５ｍｍとした。この実験では、内部の状態が観察できるように、透明アクリル製の袋状微細管を用いた。図５の結果から、いずれの径の袋状微細管においても、内空間の全体に、空気が残留することなく液が注入されていることが分かる。 FIG. 5 is a photograph showing the results of an experiment in which a liquid was injected into the inner space of the bag-like microtube using the two-stage vacuum injection device 40. The diameter of the inner space of the bag-like microtube was 200 μm, 100 μm, and 50 μm, and the length of the inner space was 5 mm. In this experiment, a transparent acrylic bag-like microtube was used so that the internal state could be observed. From the results of FIG. 5, it can be seen that in any bag-like micropipe of any diameter, the liquid is injected into the entire inner space without any air remaining.
一方、袋状の細管内に処理液を注入するための従来方法として、真空浸漬注入方法が存在する。この方法は、真空チャンバ内に予め処理液と細管とを入れた容器を配置し、その状態で真空チャンバ内を、例えば１０Ｐａ程度まで減圧した後、真空チャンバ内をパージすることによって、細管の内空間に処理液を注入する方法である。図６は、この従来方法によって袋状微細管の内空間に液体を注入した実験の結果を示す写真であり、内空間の長さを５ｍｍとし、径が３００μｍ、２００μｍ及び１００μｍの場合の各々について、液の注入状態を示している。実験結果より、内空間の径が３００μｍの袋状微細管の場合には従来方法によっても内空間の全体に液を注入することができるが、径が３００μｍより小さくなると、液が内空間を完全に満たさず、内空間の最奥部に空気が残留していることが分かる。 On the other hand, there is a vacuum dip injection method as a conventional method for injecting a treatment liquid into a bag-like thin tube. In this method, a container in which a processing solution and a thin tube are placed in advance is placed in a vacuum chamber, and the vacuum chamber is depressurized to, for example, about 10 Pa in that state, and then the inside of the thin tube is purged. In this method, a processing liquid is injected into the space. FIG. 6 is a photograph showing the results of an experiment in which a liquid was injected into the inner space of the bag-like microtubule by this conventional method, where the length of the inner space was 5 mm and the diameter was 300 μm, 200 μm and 100 μm. The liquid injection state is shown. From the experimental results, in the case of a bag-like microtube with an inner space diameter of 300 μm, the liquid can be injected into the entire inner space even by the conventional method, but when the diameter is smaller than 300 μm, the liquid completely fills the inner space. It can be seen that air remains in the innermost part of the inner space.
４．脱脂処理
袋状微細管の内空間に脱脂液が注入された後、袋状微細管の壁面の脱脂処理が行われる。袋状微細管が脱脂液に浸漬され内空間に脱脂液が注入された段階で壁面の脱脂処理が開始され、脱脂液と壁面とが接する状態を維持することにより、脱脂液の拡散作用により新たな脱脂液が壁面に供給され、脱脂が進行する。ここで、脱脂液によって浮き上がった汚れを物理的に表面から剥離させるために、超音波処理を利用することが好ましい。
4). Degreasing treatment After the degreasing liquid is injected into the inner space of the bag-like micropipe, the degreasing treatment of the wall surface of the bag-like micropipe is performed. The wall surface degreasing process is started when the bag-like microtube is immersed in the degreasing liquid and the degreasing liquid is injected into the inner space. A degreasing liquid is supplied to the wall surface and degreasing proceeds. Here, it is preferable to use ultrasonic treatment in order to physically remove the dirt floating by the degreasing liquid from the surface.
脱脂処理は、以下のように行われる。まず、袋状微細管が脱脂液に浸漬され、袋状微細管の内空間に脱脂液が注入された後、脱脂液と脱脂液に浸漬された状態の袋状微細管とが入った容器（図４における容器４７）を超音波槽内に設置する。超音波槽は、市販の超音波槽（例えば、本多電子株式会社の超音波洗浄機Ｗ−１１５）を用いることができる。超音波槽内の温度は、脱脂液の使用温度（本発明の一実施形態においては、例えば５５℃）に設定される。脱脂液の使用温度に設定された超音波槽において、適当な時間（本発明の一実施形態においては、例えば約１０分間）超音波処理を行う。 A degreasing process is performed as follows. First, after the bag-like micropipe is immersed in the degreasing liquid and the degreasing liquid is injected into the inner space of the bag-like micropipe, the container containing the degreasing liquid and the bag-like micropipe that is immersed in the degreasing liquid ( The container 47) in FIG. 4 is installed in the ultrasonic bath. As the ultrasonic tank, a commercially available ultrasonic tank (for example, an ultrasonic cleaner W-115 manufactured by Honda Electronics Co., Ltd.) can be used. The temperature in the ultrasonic bath is set to the operating temperature of the degreasing liquid (for example, 55 ° C. in one embodiment of the present invention). In an ultrasonic bath set to the operating temperature of the degreasing liquid, ultrasonic treatment is performed for an appropriate time (for example, about 10 minutes in one embodiment of the present invention).
なお、後述する工程、例えば水による洗浄処理工程、エッチング液によるエッチング処理工程などにおいて、処理時間を短縮することを目的として、処理液（例えば洗浄液、エッチング液）を拡散させることが必要な場合がある。この場合においても超音波処理が利用されることが好ましく、その方法及び装置は、上述の脱脂処理において説明したものと同様の方法及び装置とすることができる。 In addition, in a process described later, for example, a cleaning process with water, an etching process with an etchant, or the like, it may be necessary to diffuse a processing liquid (for example, a cleaning liquid or an etching liquid) for the purpose of shortening the processing time. is there. Also in this case, it is preferable to use ultrasonic treatment, and the method and apparatus thereof can be the same method and apparatus as those described in the above degreasing treatment.
５．洗浄処理
脱脂処理が終了した後、次の処理を行うために脱脂液を洗浄する必要がある。洗浄処理は、本発明の一実施形態においては以下のように行われる。まず、脱脂処理工程において用いられた脱脂液と袋状微細管とが入った容器から、脱脂液のみを除去する。この際、袋状微細管の内空間に空気を入れないために、袋状微細管の少なくとも内空間が外気に触れない状態で、すなわち袋状微細管の少なくとも内空間が脱脂液の液面から露出しない程度の量の脱脂液が容器内に残るように、脱脂液を除去する。次に、ある程度の量の脱脂液を捨てた容器内に洗浄液を入れ（この時点では、洗浄液と脱脂液とが混合した液体が容器内に存在することになる）、撹拌することによって、容器内の袋状微細管及び容器の内壁を洗浄液で洗浄する。洗浄液は、例えば純水であることが好ましい。再び、袋状微細管の少なくとも内空間が脱脂液と洗浄液との混合液から露出しない程度の量の液体が容器内に残るように、容器内の液体を除去する。さらに容器内に洗浄液を入れ、同様に袋状微細管と容器とを洗浄する。洗浄液の投入、洗浄、及び除去は、脱脂液の泡が消えるまで行うことが好ましく、理想的には３回以上行うことが好ましい。その後、好ましくは、袋状微細管と洗浄液とが入った容器を超音波槽内に配置し、適当な時間（本発明の一実施形態においては、例えば約５分間）超音波による置換洗浄を行う。
5. Cleaning process After the degreasing process is completed, it is necessary to clean the degreasing liquid in order to perform the next process. The cleaning process is performed as follows in one embodiment of the present invention. First, only the degreasing liquid is removed from the container containing the degreasing liquid and the bag-like microtube used in the degreasing process. At this time, in order to prevent air from entering the inner space of the bag-like micropipe, at least the inner space of the bag-like micropipe is not in contact with the outside air, that is, at least the inner space of the bag-like micropipe is from the liquid surface of the degreasing liquid. The degreasing liquid is removed so that an amount of the degreasing liquid not exposed is left in the container. Next, the cleaning liquid is put into a container in which a certain amount of the degreasing liquid is discarded (at this point, the liquid in which the cleaning liquid and the degreasing liquid are mixed is present in the container), and the container is stirred. The bag-like microtube and the inner wall of the container are washed with a washing solution. The cleaning liquid is preferably pure water, for example. Again, the liquid in the container is removed such that an amount of liquid remains in the container so that at least the inner space of the bag-like microtubule is not exposed from the mixture of the degreasing liquid and the cleaning liquid. Further, a cleaning liquid is put into the container, and the bag-like microtube and the container are cleaned in the same manner. The washing liquid is preferably added, washed, and removed until the bubbles of the degreasing liquid disappear, and ideally, it is preferably carried out three times or more. Thereafter, preferably, the container containing the bag-like microtubule and the cleaning liquid is placed in the ultrasonic bath, and the replacement cleaning is performed by ultrasonic waves for an appropriate time (for example, about 5 minutes in one embodiment of the present invention). .
この処理において、袋状微細管の内空間に空気を入れないために、袋状微細管の少なくとも内空間が液から露出しない程度の量の液が容器内に残るように液を除去することの意味は、以下のとおりである。すなわち、本発明における課題の一つは、袋状微細管の微小な内空間に、メッキ膜形成工程において必要な各種の処理液を如何に注入するかということである。その課題を解決するため、本発明においては、上述した新規な２段階真空注入方法を採用している。ところが、メッキ膜形成工程においては処理ごとに処理液を交換することが必要であり、処理液の交換ごとに２段階真空注入方法を行うことは現実的ではない。そこで、本発明においては、一旦２段階真空注入方法によって袋状微細管の内空間に処理液を注入した後は、次に袋状微細管の内空間に空気を入れることが必要となるまで（例えば、内空間の壁面を乾燥させることが必要となるまで）、処理液の交換の際に少なくとも内空間が空気に露出しないようにする。このように処理することによって、袋状微細管の内空間全体にわたって容易に処理液を置換することができる。 In this process, in order to prevent air from entering the inner space of the bag-like microtube, the liquid is removed so that at least the inner space of the bag-like microtubule remains in the container. The meaning is as follows. That is, one of the problems in the present invention is how to inject various processing liquids necessary in the plating film forming process into the minute inner space of the bag-like microtube. In order to solve the problem, in the present invention, the above-described novel two-stage vacuum injection method is adopted. However, in the plating film forming step, it is necessary to exchange the treatment liquid for each treatment, and it is not realistic to perform the two-stage vacuum injection method every time the treatment solution is exchanged. Therefore, in the present invention, after the treatment liquid is once injected into the inner space of the bag-like microtubule by the two-stage vacuum injection method, until it is necessary to put air into the inner space of the bag-like microtube ( For example, until it is necessary to dry the wall surface of the inner space), at least the inner space should not be exposed to the air when the processing liquid is replaced. By processing in this way, the processing liquid can be easily replaced over the entire inner space of the bag-like micropipe.
６．エッチング処理
脱脂が終了し、脱脂液が洗浄された袋状微細管は、次にエッチング処理が行われることが好ましい。エッチング処理は、袋状微細管の壁面を粗化することによって壁面とメッキ膜との密着性を向上させることを目的として行われる。前の洗浄処理工程において洗浄が終了した微細管と洗浄液とが入った容器から、少なくとも微細管の内空間が露出しないように洗浄液を除去し、容器内にエッチング溶液を入れる。エッチング溶液は、限定されるものではなく、市販のエッチング溶液（例えば、菱江化学株式会社のＣＰＢ−４０）を用いることができる。洗浄液とエッチング溶液との混合液を容器から除去し、容器内にエッチング溶液を入れる作業を、複数回繰り返してもよい。袋状微細管とエッチング溶液とが入った容器を超音波槽内に配置し、超音波を当てながら、適当な時間（本発明の一実施形態においては、例えば約１分間）エッチング処理を行う。
6). Etching Treatment It is preferable that the bag-shaped microtubule after the degreasing is finished and the degreasing liquid is washed is then subjected to an etching treatment. The etching process is performed for the purpose of improving the adhesion between the wall surface and the plating film by roughening the wall surface of the bag-like micropipe. The cleaning liquid is removed from the container containing the micropipe and the cleaning liquid that have been cleaned in the previous cleaning process so that at least the inner space of the micropipe is not exposed, and the etching solution is put into the container. The etching solution is not limited, and a commercially available etching solution (for example, CPB-40 manufactured by Hiejiang Chemical Co., Ltd.) can be used. The operation of removing the liquid mixture of the cleaning liquid and the etching solution from the container and putting the etching solution into the container may be repeated a plurality of times. The container containing the bag-like microtube and the etching solution is placed in an ultrasonic bath, and the etching process is performed for an appropriate time (for example, about 1 minute in one embodiment of the present invention) while applying ultrasonic waves.
７．洗浄処理
エッチング処理の終了後、超音波槽から容器を取り出し、上述の洗浄処理において説明された方法と同様の方法で洗浄処理を行う。すなわち、容器内の袋状微細管の少なくとも内空間が露出しない程度に容器内の液を除去して容器内に洗浄液を入れることを繰り返しながら、洗浄を行う。その後、好ましくは、超音波層において置換洗浄を行う。
7). Cleaning Process After the etching process is completed, the container is taken out from the ultrasonic bath and the cleaning process is performed in the same manner as described in the above cleaning process. That is, the cleaning is performed while repeatedly removing the liquid in the container and putting the cleaning liquid in the container so that at least the inner space of the bag-like microtubule in the container is not exposed. Thereafter, it is preferable to perform substitution cleaning in the ultrasonic layer.
８．活性化処理
エッチング処理が終了し、エッチング液が洗浄された袋状微細管は、次に活性化処理が行われることが好ましい。活性化処理は、袋状微細管の壁面に生成された酸化膜を除去することを目的として行われる。前の洗浄工程において洗浄処理が終了した袋状微細管と洗浄液とが入った容器から、少なくとも袋状微細管の内空間が露出しないように洗浄液を除去し、容器内に活性化溶液を入れる。活性化溶液は、限定されるものではなく、市販の活性化溶液（例えば、市販の塩酸３５％と純水とを１：１で混合した溶液）を用いることができる。洗浄液と活性化溶液との混合液を容器から除去し、容器内に活性化溶液を入れる作業を、複数回繰り返してもよい。袋状微細管と活性化溶液とが入った容器を超音波槽内に配置し、超音波を当てながら、適当な時間（本発明の一実施形態においては、例えば約１分間）活性化処理を行う。
8). Activation Treatment After the etching treatment is completed, the bag-shaped microtubule from which the etching solution has been washed is preferably subjected to an activation treatment. The activation treatment is performed for the purpose of removing the oxide film generated on the wall surface of the bag-like microtube. The cleaning liquid is removed from the container containing the bag-like micropipe and the cleaning liquid which have been cleaned in the previous cleaning step so that at least the inner space of the bag-like micropipe is not exposed, and the activation solution is put into the container. The activation solution is not limited, and a commercially available activation solution (for example, a solution in which 35% of commercially available hydrochloric acid and pure water are mixed at 1: 1) can be used. The operation of removing the mixed solution of the cleaning liquid and the activation solution from the container and placing the activation solution in the container may be repeated a plurality of times. The container containing the bag-like microtube and the activation solution is placed in an ultrasonic bath, and the activation treatment is performed for an appropriate time (for example, about 1 minute in one embodiment of the present invention) while applying ultrasonic waves. Do.
９．洗浄処理
活性化処理の終了後、超音波槽から容器を取り出し、上述の洗浄処理において説明された方法と同様の方法で洗浄処理を行う。すなわち、容器内袋状の微細管の少なくとも内空間が露出しない程度に容器内の液を除去して容器内に洗浄液を入れることを繰り返しながら、洗浄を行う。その後、好ましくは、超音波層において置換洗浄を行う。
9. Cleaning Process After the activation process is completed, the container is taken out from the ultrasonic bath and the cleaning process is performed in the same manner as described in the above cleaning process. That is, the cleaning is performed by repeatedly removing the liquid in the container and placing the cleaning liquid in the container to such an extent that at least the inner space of the bag-like fine tube in the container is not exposed. Thereafter, it is preferable to perform substitution cleaning in the ultrasonic layer.
１０．ニッケルメッキ膜形成処理
次に、脱脂処理が終了した袋状微細管、又は、エッチング処理及び活性化処理が終了した袋状微細管の内壁及び外壁に、ニッケルメッキ膜を形成する。脱脂処理後においても、エッチング処理及び活性化処理後においても、洗浄液による洗浄処理が行われている。従って、ニッケルメッキ膜形成処理の前には、洗浄処理の終了した袋状微細管が洗浄液に浸漬した状態で容器内に入っている。ニッケルメッキ膜形成処理においては、まず、容器内の洗浄液とニッケルメッキ液とを置換する。置換は、上述の洗浄処理において説明された方法と同様の方法で行う。すなわち、容器内の袋状微細管の少なくとも内空間が洗浄液から露出しない程度に容器内の洗浄液を容器から除去し、容器内にニッケルメッキ液を入れる。洗浄液とニッケルメッキ液との混合液を容器から除去し、容器にニッケルメッキ液を追加する工程を、複数回繰り返してもよい。微細管とニッケルメッキ液とが入った容器を超音波槽内に配置し、超音波を当てながら、適当な時間（本発明の一実施形態においては、例えば約１０分間）ニッケルメッキ液の置換処理を行う。超音波を当てることによって、袋状微細管の内部の金属塩濃度と外部の濃度とを均一にすることができる。
10. Nickel plating film formation process Next, a nickel plating film is formed on the inner wall and the outer wall of the bag-shaped micropipe that has been degreased or the bag-shaped micropipe that has been subjected to the etching process and the activation process. Even after the degreasing treatment and after the etching treatment and the activation treatment, the washing treatment with the washing liquid is performed. Therefore, before the nickel plating film forming process, the bag-like micropipe that has been cleaned is placed in the container in a state of being immersed in the cleaning solution. In the nickel plating film forming process, first, the cleaning liquid in the container and the nickel plating liquid are replaced. The replacement is performed by a method similar to the method described in the above cleaning process. That is, the cleaning liquid in the container is removed from the container to such an extent that at least the inner space of the bag-like microtube in the container is not exposed from the cleaning liquid, and the nickel plating liquid is put into the container. The process of removing the mixed liquid of the cleaning liquid and the nickel plating liquid from the container and adding the nickel plating liquid to the container may be repeated a plurality of times. A container containing a fine tube and a nickel plating solution is placed in an ultrasonic bath, and the nickel plating solution is replaced for a suitable time (for example, about 10 minutes in one embodiment of the present invention) while applying ultrasonic waves. I do. By applying ultrasonic waves, the metal salt concentration inside the bag-like microtube and the external concentration can be made uniform.
ニッケルメッキ液は、限定されるものではなく、例えば、硫酸ニッケル、塩化ニッケル及びホウ酸を主成分とするワット浴などのような一般的なニッケルメッキ液を用いることができる。本発明の一実施形態においては、ニッケルメッキ液として、１種又は数種類の市販の光沢剤を添加した光沢ニッケルメッキ液を用いることが好ましい。 The nickel plating solution is not limited. For example, a general nickel plating solution such as a Watt bath mainly composed of nickel sulfate, nickel chloride, and boric acid can be used. In one embodiment of the present invention, it is preferable to use a bright nickel plating solution to which one or several kinds of commercially available brighteners are added as the nickel plating solution.
なお、ニッケルメッキ膜の形成前に、洗浄液を乾燥させておくことも可能である。その場合には、乾燥終了後には、袋状微細管の内空間には空気が存在しているため、上述の脱脂液の注入又は後述する金メッキ液の注入と同様に、２段階真空注入方法を利用して内空間にニッケルメッキ液を注入することになる。 It is also possible to dry the cleaning solution before forming the nickel plating film. In that case, since air exists in the inner space of the bag-like micropipe after the completion of drying, the two-stage vacuum injection method is used similarly to the above-described degreasing liquid injection or gold plating liquid injection described later. Utilizing this, the nickel plating solution is injected into the inner space.
次いで、袋状微細管とニッケルメッキ液とが入った容器を超音波槽から取り出し、パルスリバース電気メッキ処理を行う。パルスリバース電気メッキ処理には、バレルメッキ方法を用いることが好ましい。通常は、電気メッキ処理においては、直流電源を用いて直流電流によってメッキ処理が行われる。しかしながら、本発明が対象とする袋状の微小内空間を有する微細管の場合には、通常の直流電源による電気メッキによる処理では、生成されるメッキ膜の厚さが内空間の入り口の部分と奥の部分とで異なることがある。これは、微小な内空間を有する袋状微細管においては、袋状微細管の内壁面全体で電流密度に差が生じ、表面への金属析出が不均一になることが原因と考えられる。例えば、内面のメッキ膜の厚さが不十分な袋状微細管の場合には、耐食性や褶動による摩耗への耐久性が下がる。また、開口部付近のメッキ膜の厚さが厚い場合には、外形寸法が変わる、内径の狭まりによりプランジャが入らなくなるといった問題が生じる可能性がある。そこで、本発明においては、電気メッキ処理の方法としてパルスリバース電気メッキ処理を行う。 Next, the container containing the bag-like fine tube and the nickel plating solution is taken out of the ultrasonic bath and subjected to pulse reverse electroplating. A barrel plating method is preferably used for the pulse reverse electroplating process. Usually, in the electroplating process, the plating process is performed by a direct current using a direct current power source. However, in the case of a microtube having a bag-shaped minute inner space that is the subject of the present invention, in the treatment by electroplating with a normal DC power supply, the thickness of the plating film to be generated is different from the entrance portion of the inner space. It may be different in the back part. This is considered to be because, in a bag-shaped microtube having a minute inner space, a difference in current density occurs across the entire inner wall surface of the bag-shaped microtube, resulting in non-uniform metal deposition on the surface. For example, in the case of a bag-like micropipe having an insufficient thickness of the plating film on the inner surface, corrosion resistance and durability against vibration due to peristalsis are reduced. Further, when the thickness of the plating film in the vicinity of the opening is thick, there is a possibility that problems such as change of the outer dimensions and the inability to enter the plunger due to the narrowing of the inner diameter. Therefore, in the present invention, pulse reverse electroplating is performed as a method of electroplating.
パルスリバース電気メッキ処理は、電気メッキ装置において、直流電源に代えてパルス電源を用い、電流の方向を周期的に変えながら行うメッキ処理である。パルスリバース電気メッキ処理においては、袋状微細管の壁面に一旦形成されたメッキ膜が、逆方向の電流を流すことによってイオン化され、メッキ液に戻る。メッキ膜がイオン化される際には、形成されたメッキ膜の厚みが厚い部分、すなわち高電部から優先的にイオン化されるため、最終的には均一な厚みのメッキ膜が全体に形成されることになる。図７は、袋状微細管に、通常の直流電源による電気メッキ処理によってニッケルメッキ膜を形成した場合（図７Ａ）と、パルス電源によるパルスリバース電気メッキ処理によってニッケルメッキ膜を形成した場合（図７Ｂ）と示す写真である。図７Ａは、電流密度１Ａ／ｄｍ２、反応時間３０分で直流電源による電気メッキ処理を行い、図７Ｂは、電流密度−３Ａ／ｄｍ２〜１Ａ／ｄｍ２、反応時間３０分、パルス幅０．５ｍｓｅｃ〜０．１ｍｓｅｃでパルス電源によるパルスリバース電気メッキ処理を行った結果である。この結果から、パルスリバース電気メッキ処理を行うことによって、均一な厚みのメッキ膜が形成されることが分かる。 The pulse reverse electroplating process is a plating process performed in an electroplating apparatus using a pulse power source instead of a DC power source and periodically changing the direction of current. In the pulse reverse electroplating process, the plating film once formed on the wall surface of the bag-like microtube is ionized by flowing a current in the reverse direction and returns to the plating solution. When the plating film is ionized, it is preferentially ionized from the thick part of the formed plating film, that is, the high voltage part, so that the plating film of uniform thickness is finally formed on the whole. It will be. FIG. 7 shows a case where a nickel-plated film is formed on a bag-like microtube by an electroplating process using a normal DC power supply (FIG. 7A) and a case where a nickel-plated film is formed by a pulse reverse electroplating process using a pulse power supply (FIG. 7). 7B). 7A shows a current density of 1 A / dm 2 and a reaction time of 30 minutes, and electroplating is performed with a DC power source. FIG. 7B shows a current density of −3 A / dm 2 to 1 A / dm 2 , a reaction time of 30 minutes, and a pulse width of 0. It is the result of performing the pulse reverse electroplating process by a pulse power supply at 0.5 msec to 0.1 msec. From this result, it is understood that a plating film having a uniform thickness is formed by performing the pulse reverse electroplating process.
本発明の一実施形態に係るパルスリバース電気メッキ処理においては、まず、洗浄後の容器内の袋状微細管とニッケルメッキ液とを回転容器（バレル）に投入する。この際、容器内のニッケルメッキ液は、袋状微細管の少なくとも内空間が液から露出しない最小限の量のみがバレルに入るようにすることが好ましい。バレル内には、洗浄処理済みのダミー材も投入する。ダミー材は、通常、バレル内において電極と袋状微細管との間を通電し、撹拌性を向上させる目的で用いられる。ニッケルメッキ浴槽内でバレルを回転させながら、バレル外部の浴槽内に設置されたニッケル電極と袋状微細管との間にパルス電源を用いて周期的に方向が変化する電流を流すことによって、袋状微細管の内外壁表面に均一な厚みのニッケルメッキ膜が形成される。パルスリバース電気メッキ装置は、市販の装置（例えば、北斗電工株式会社のＨＣＰ−３０１Ｈ）を用いることができる。本発明の一実施形態においては、例えば、内径１００μｍ、内空間の長さ１３００μｍ、外径１６０μｍ、長さ１４５０μｍの微細管にメッキ膜を形成する場合には、電流密度−３Ａ／ｄｍ２〜１Ａ／ｄｍ２、反応時間３０分、パルス幅０．５ｍｓｅｃ〜０．１ｍｓｅｃという条件でパルスリバース電気メッキ処理が行われることが好ましい。 In the pulse reverse electroplating process according to one embodiment of the present invention, first, the bag-like micropipe and the nickel plating solution in the cleaned container are put into a rotating container (barrel). At this time, it is preferable that the nickel plating solution in the container enters only the minimum amount that does not expose at least the inner space of the bag-like micropipe from the solution. A dummy material that has been cleaned is also put into the barrel. The dummy material is usually used for the purpose of energizing between the electrode and the bag-like microtube in the barrel to improve the stirring ability. By rotating a barrel in a nickel-plated bath and passing a current whose direction changes periodically using a pulse power source between the nickel electrode installed in the bath outside the barrel and the bag-like microtube, A nickel plating film having a uniform thickness is formed on the inner and outer wall surfaces of the fine tube. As the pulse reverse electroplating apparatus, a commercially available apparatus (for example, HCP-301H manufactured by Hokuto Denko Co., Ltd.) can be used. In one embodiment of the present invention, for example, when a plating film is formed on a microtube having an inner diameter of 100 μm, an inner space length of 1300 μm, an outer diameter of 160 μm, and a length of 1450 μm, a current density of −3 A / dm 2 to 1 A. It is preferable that the pulse reverse electroplating process is performed under the conditions of / dm 2 , reaction time of 30 minutes, and pulse width of 0.5 msec to 0.1 msec.
１１．洗浄処理
ニッケルメッキ膜の形成後、バレルからメッキ液ごと袋状微細管を容器に取り出し、上述の洗浄処理において説明された方法と同様の方法で洗浄処理を行う。すなわち、容器内の袋状微細管の少なくとも内空間が液から露出しない程度に容器内の液を除去して容器内に洗浄液を入れることを繰り返しながら、洗浄を行う。その後、好ましくは、超音波層において置換洗浄を行う。
11. Cleaning Process After the nickel plating film is formed, the bag-shaped microtube together with the plating solution is taken out from the barrel into the container, and the cleaning process is performed in the same manner as described in the above cleaning process. That is, the cleaning is performed while repeatedly removing the liquid in the container and putting the cleaning liquid in the container so that at least the inner space of the bag-like microtubule in the container is not exposed from the liquid. Thereafter, it is preferable to perform substitution cleaning in the ultrasonic layer.
１２．２段階真空注入装置による金メッキ液の注入
ニッケルメッキ膜が形成された袋状微細管の表面には、次に金メッキ膜が形成される。金メッキ膜の形成処理に進む前には、袋状微細管の内外壁の表面を一旦乾燥させる必要がある。乾燥の方法は特に限定されるものではないが、この後に必要となる金メッキ液の注入に、脱脂液の注入の際に行われた方法と同様の２段階真空注入方法を利用することになるため、洗浄後の袋状微細管を図４に示される２段階真空注入装置の真空チャンバ４１に入れて真空乾燥させることが好ましい。まず、洗浄が終了した袋状微細管４６を容器４７に入れ、真空チャンバ４１内に配置する。容器４７の内部と連通されたパイプ４２を介して接続された容器４３内には金メッキ液４４を入れる。パイプ４２に設けられたバルブ４５を閉じて、真空チャンバ内の空気を真空ポンプ（図示せず）によって排出口４９から排出する。そのまま、真空チャンバ４１内が十分な真空雰囲気になり（本発明の一実施形態においては、１０Ｐａ程度）、微細管が乾燥状態となるまで（本発明の一実施形態においては、例えば約３０分〜１時間）待機する。
12.2 Injection of Gold Plating Solution Using a Vacuum Injection Device Next, a gold plating film is formed on the surface of the bag-like microtube on which the nickel plating film is formed. Before proceeding to the gold plating film formation process, it is necessary to once dry the surfaces of the inner and outer walls of the bag-like micropipe. The drying method is not particularly limited, but a two-stage vacuum injection method similar to the method performed at the time of injecting the degreasing solution is used for injecting the gold plating solution necessary thereafter. The bag-like micropipe after washing is preferably placed in a vacuum chamber 41 of a two-stage vacuum injection apparatus shown in FIG. First, the bag-like micropipe 46 that has been cleaned is placed in a container 47 and placed in the vacuum chamber 41. A gold plating solution 44 is placed in a container 43 connected via a pipe 42 communicating with the inside of the container 47. The valve 45 provided in the pipe 42 is closed, and the air in the vacuum chamber is discharged from the discharge port 49 by a vacuum pump (not shown). As it is, the inside of the vacuum chamber 41 becomes a sufficient vacuum atmosphere (in one embodiment of the present invention, about 10 Pa), and the microtube is in a dry state (in one embodiment of the present invention, for example, about 30 minutes to 1 hour) Wait.
袋状微細管が十分に乾燥した後、バルブ４５を開放して金メッキ液４４を容器４７内に供給する。金メッキ液は、市販の金メッキ液（例えば、メルテックス株式会社のオウロナール４４ＢＣ）を用いることができる。金メッキ液４４は、容器４７内において袋状微細管４６全体が金メッキ液４４に浸漬するのに十分な量が供給される。容器４７内の袋状微細管４６が金メッキ液４４に十分に浸漬されたことを確認した後、バルブ４８を開放し（パージする）、真空ポンプを停止する。この方法によれば、真空チャンバ４１内を真空雰囲気にすることで袋状微細管４６の内空間に滞留している空気が排出されるため、容器４７内に金メッキ液４４が供給されたときに金メッキ液４４が袋状微細管４６の内空間に入り込む。この時点でも金メッキ液４４は袋状微細管４６の内空間に注入されているが、次に真空チャンバ４１内に空気が導入されたときに、より確実に金メッキ液４４が袋状微細管４６の内空間に押し込まれることになる。 After the bag-like micropipe is sufficiently dried, the valve 45 is opened and the gold plating solution 44 is supplied into the container 47. As the gold plating solution, a commercially available gold plating solution (for example, Ouronal 44BC manufactured by Meltex Co., Ltd.) can be used. The gold plating solution 44 is supplied in an amount sufficient to immerse the entire bag-like micropipe 46 in the gold plating solution 44 in the container 47. After confirming that the bag-like micropipe 46 in the container 47 is sufficiently immersed in the gold plating solution 44, the valve 48 is opened (purged) and the vacuum pump is stopped. According to this method, the air staying in the inner space of the bag-like micropipe 46 is discharged by making the inside of the vacuum chamber 41 a vacuum atmosphere, so that the gold plating solution 44 is supplied into the container 47. The gold plating solution 44 enters the inner space of the bag-like micropipe 46. Even at this time, the gold plating solution 44 is injected into the inner space of the bag-like microtube 46, but when the air is next introduced into the vacuum chamber 41, the gold plating solution 44 is more reliably transferred to the bag-like microtube 46. It will be pushed into the inner space.
１３．金メッキ膜の形成処理
金メッキ膜の形成は、上述のニッケルメッキ膜の形成と同様に、パルスリバース電気メッキによって行われる。一実施形態においては、パルスリバース電気メッキ処理は、バレルメッキ方法を用いることが好ましい。まず、金メッキ液注入後の容器内の袋状微細管と金メッキ液とをバレルに投入する。この際、容器内の金メッキ液は、袋状微細管の少なくとも内空間が液から露出しない最小限の量のみがバレルに入るようにすることが好ましい。バレル内には、洗浄処理済みのダミー材も投入する。次いで、袋状微細管及びダミー材が投入されたバレルを金メッキ浴槽内で回転させながら、バレル外部の浴槽内に設置された金電極と袋状微細管との間にパルス電源を用いて周期的に方向が変化する電流を流すことによって、袋状微細管の内外壁表面に均一な厚みの金メッキ膜が形成される。本発明の一実施形態においては、例えば、ニッケルメッキ膜が形成された上述の微細管に金メッキ膜を形成する場合には、電流密度−０．３Ａ／ｄｍ２〜０．１Ａ／ｄｍ２、反応時間８０分、パルス幅０．５ｍｓｅｃ〜０．１ｍｓｅｃという条件でパルスリバース電気メッキ処理が行われることが好ましい。
13. Gold Plated Film Forming Process The gold plated film is formed by pulse reverse electroplating in the same manner as the nickel plated film. In one embodiment, the pulse reverse electroplating process preferably uses a barrel plating method. First, the bag-like fine tube and the gold plating solution in the container after the gold plating solution are injected are put into the barrel. At this time, it is preferable that the gold plating solution in the container enters only the minimum amount that does not expose at least the inner space of the bag-like microtube from the solution. A dummy material that has been cleaned is also put into the barrel. Next, while rotating the barrel filled with the bag-like microtube and the dummy material in the gold-plated bath, periodically using a pulse power source between the gold electrode installed in the bath outside the barrel and the bag-like microtube By flowing an electric current whose direction changes, a gold plating film having a uniform thickness is formed on the inner and outer wall surfaces of the bag-like microtube. In one embodiment of the present invention, for example, when a gold plating film is formed on the above-described microtube on which a nickel plating film is formed, the current density is −0.3 A / dm 2 to 0.1 A / dm 2 , the reaction It is preferable that the pulse reverse electroplating process is performed under the conditions of a time of 80 minutes and a pulse width of 0.5 msec to 0.1 msec.
１４．洗浄処理
金メッキ膜の形成後、バレルからメッキ液ごと袋状微細管を容器に取り出し、上述の洗浄処理において説明された方法と同様の方法で洗浄処理を行う。すなわち、容器内の袋状微細管の少なくとも内空間が露出しない程度に容器内の液を除去して容器内に洗浄液を入れることを繰り返しながら、洗浄を行う。洗浄処理の終了後、袋状微細管を洗浄液から取り出し、乾燥させる。
14 Cleaning process After the gold plating film is formed, the bag-like micropipe together with the plating solution is taken out from the barrel into the container, and the cleaning process is performed in the same manner as described in the above cleaning process. That is, the cleaning is performed while repeatedly removing the liquid in the container and putting the cleaning liquid in the container so that at least the inner space of the bag-like microtubule in the container is not exposed. After completion of the cleaning process, the bag-like microtube is taken out of the cleaning liquid and dried.
（実施例）
図８に、本発明の一実施形態に係る方法によって作成された、均一な厚さのニッケルメッキ膜及び金メッキ膜が生成された袋状微細管の断面を示す。このメッキ膜は、本明細書における発明を実施するための形態に記載された、上述の本発明の一実施形態による方法、装置、及び条件を用いて作成されたものである。図８から、袋状微細管の内壁面にメッキ切れを起こすことなく概ね均一のメッキ膜が形成されていることが分かる。メッキ膜の厚さは、袋状微細管の開口部（図８において袋状微細管の右側）から４００μｍ、８００μｍ、及び１２００μｍの位置で、ニッケルメッキ膜の厚さは、それぞれ１．１７μｍ、０．４５４μｍ、及び０．５５６μｍであり、金メッキ膜の厚さは、それぞれ０．１４μｍ、０．０２５μｍ、及び０．１０４μｍであった。
(Example)
FIG. 8 shows a cross-section of a bag-shaped microtubule produced by a method according to an embodiment of the present invention and having a nickel plating film and a gold plating film having a uniform thickness. This plated film is created using the method, apparatus, and conditions according to the above-described embodiment of the present invention described in the mode for carrying out the invention in this specification. It can be seen from FIG. 8 that a substantially uniform plating film is formed on the inner wall surface of the bag-shaped microtubule without causing plating failure. The thickness of the plating film is 400 μm, 800 μm, and 1200 μm from the opening of the bag-like microtube (on the right side of the bag-like microtube in FIG. 8), and the thickness of the nickel plating film is 1.17 μm, 0, respectively. The thicknesses of the gold plating films were 0.14 μm, 0.025 μm, and 0.104 μm, respectively.
（比較例１）
図９は、従来の処理液注入方法を用いて脱脂液及びメッキ液が注入された場合の袋状微細管の断面を示す写真である。図９は、内径３５０μｍ、奥行き１８００μｍのベリリウム鋼の袋状細管に、ニッケルメッキ膜を形成したものである。ニッケルメッキ膜の形成方法は以下のとおりである。まず、本明細書において従来の処理液注入方法として上述された真空浸漬注入方法を用いて、袋状細管の内空間に脱脂液を注入した。次に、本明細書において上述された方法と同じ脱脂処理、洗浄処理、エッチング処理、洗浄処理、活性化処理、及び洗浄処理を行った。次に、袋状細管の入った容器にニッケルメッキ液を入れ、本明細書において上述された真空浸漬注入方法を用いて、袋状細管の内空間にニッケルメッキ液を注入した。最後に、直流電源による電気メッキ処理（電流密度１Ａ／ｄｍ２、反応時間３０分）を行った。各処理液は、本明細書において上述されたものを用いた。従来の真空浸漬注入方法では、図６に示されるように細管の内空間の最奥部に空気が残留するため、この部分には脱脂液やメッキ液などの処理液が到達せず、結果として、この部分（図９における袋状微細管の内空間の左側端部における黒っぽい部分）にメッキ不良（メッキ切れ）が生じたことが分かる。
(Comparative Example 1)
FIG. 9 is a photograph showing a cross section of the bag-like microtubule when the degreasing solution and the plating solution are injected using the conventional processing solution injection method. FIG. 9 shows a beryllium steel bag-like tubule having an inner diameter of 350 μm and a depth of 1800 μm formed with a nickel plating film. The method for forming the nickel plating film is as follows. First, a degreasing solution was injected into the inner space of the bag-like tubule using the vacuum immersion injection method described above as a conventional treatment solution injection method in this specification. Next, the same degreasing treatment, cleaning treatment, etching treatment, washing treatment, activation treatment, and washing treatment as those described above in this specification were performed. Next, the nickel plating solution was put into a container containing the bag-like tubule, and the nickel plating solution was injected into the inner space of the bag-like tubule by using the vacuum dip injection method described above in this specification. Finally, an electroplating process using a DC power source (current density 1 A / dm 2 , reaction time 30 minutes) was performed. Each processing solution used was the one described above in this specification. In the conventional vacuum dip injection method, as shown in FIG. 6, air remains in the innermost part of the inner space of the narrow tube, so that the processing liquid such as the degreasing liquid or the plating liquid does not reach this part. It can be seen that plating failure (out of plating) occurred in this portion (the dark portion at the left end of the inner space of the bag-like microtube in FIG. 9).
（比較例２）
本明細書において上述したように、図７は、直流電源による電気メッキ処理（直流メッキ法）によって微細管にニッケルメッキ膜を形成した場合と、パルス電源によるパルスリバース電気メッキ処理（ＰＲメッキ法）によってニッケルメッキ膜を形成した場合とを比較した結果である。図７から、上述のとおり、パルスリバース電気メッキ処理を行わない場合には、均一な厚みのメッキ膜が形成されないことが分かる。
(Comparative Example 2)
As described above in this specification, FIG. 7 shows a case where a nickel plating film is formed on a fine tube by an electroplating process using a DC power source (DC plating method) and a pulse reverse electroplating process using a pulse power source (PR plating method). It is the result compared with the case where a nickel plating film is formed by. As can be seen from FIG. 7, when the pulse reverse electroplating process is not performed, a plating film having a uniform thickness is not formed.
４０：２段階真空注入装置
４１：真空チャンバ
４２：パイプ
４３、４７：容器
４４：液
４５：バルブ
４６：微細管
４８：大気導入手段
４９：排気手段
40: Two-stage vacuum injection device 41: Vacuum chamber 42: Pipe 43, 47: Container 44: Liquid 45: Valve 46: Fine tube 48: Atmospheric introduction means 49: Exhaust means
Claims (6)
真空雰囲気内に配置された微細管にプラズマを照射することにより、前記微細管の内壁及び外壁の表面の不純物を除去する、プラズマ洗浄工程と、
不純物が除去され内空間に空気が残留していない状態の真空雰囲気内の前記微細管を脱脂液に浸漬させ、真空雰囲気を大気圧雰囲気に置換することにより、前記微細管の前記内空間の全体に脱脂液を注入し、前記微細管の前記内壁及び外壁の脱脂処理を行う、脱脂工程と、
脱脂された前記微細管の少なくとも前記内空間に空気が入らないようにしながら脱脂液を洗浄液に置換し、前記微細管を洗浄する、脱脂液洗浄工程と、
洗浄後の前記微細管にパルスリバース電気メッキ処理を行う、メッキ工程と、
を含むことを特徴とする方法。 A method of forming a plating film on the outer wall of the microtube with one end closed and the inner wall of the inner space,
A plasma cleaning step of removing impurities on the inner wall and the outer wall of the microtube by irradiating the microtube arranged in a vacuum atmosphere with plasma;
By immersing the fine tube in a vacuum atmosphere in a state where impurities are removed and no air remains in the inner space in a degreasing liquid, and replacing the vacuum atmosphere with an atmospheric pressure atmosphere, the entire inner space of the fine tube A degreasing step of injecting a degreasing liquid into the microtube and performing a degreasing treatment on the inner wall and the outer wall of the microtube;
A degreasing liquid washing step of replacing the degreasing liquid with a washing liquid while preventing air from entering at least the inner space of the degreased fine pipe, and washing the fine pipe;
A plating process for performing pulse reverse electroplating on the microtubule after washing; and
A method comprising the steps of:
前記脱脂液洗浄工程において洗浄された前記微細管を乾燥する工程と、
乾燥された前記微細管を真空雰囲気内に配置した後、前記内空間に空気が残留していない状態の真空雰囲気内の前記微細管をメッキ液に浸漬させ、真空雰囲気を大気圧雰囲気に置換することにより、前記微細管の前記内空間の全体に前記メッキ液を注入する工程と、
を含むことを特徴とする、請求項１に記載の方法。 The plating process includes
Drying the fine tube washed in the degreasing liquid washing step;
After the dried micro tube is placed in a vacuum atmosphere, the micro tube in the vacuum atmosphere with no air remaining in the inner space is immersed in a plating solution, and the vacuum atmosphere is replaced with an atmospheric pressure atmosphere. Injecting the plating solution into the entire inner space of the microtube,
The method of claim 1, comprising:
洗浄された前記微細管を乾燥させる工程と、
乾燥された前記微細管を真空雰囲気内に配置した後、前記内空間に空気が残留していない状態の前記微細管を前記メッキ工程で用いたメッキ液とは別のメッキ液に浸漬させ、真空雰囲気を大気圧雰囲気に置換することにより、前記微細管の前記内空間の全体に前記別のメッキ液を注入する工程と、
前記微細管に前記別のメッキ液によるパルスリバース電気メッキ処理を行う工程と、
をさらに含むことを特徴とする、請求項１から請求項３のいずれかに記載の方法。 After the plating step, washing the fine tube with a cleaning liquid while preventing air from entering at least the inner space of the plated fine tube;
Drying the washed microtubules;
After placing the dried microtube in a vacuum atmosphere, the microtube in a state where no air remains in the inner space is immersed in a plating solution different from the plating solution used in the plating step, and vacuum Injecting the other plating solution into the entire inner space of the microtube by replacing the atmosphere with an atmospheric pressure atmosphere; and
Performing a pulse reverse electroplating process on the fine tube with the other plating solution;
The method according to claim 1, further comprising:
エッチングされた前記微細管の少なくとも前記内空間に空気が入らないようにしながらエッチング液を洗浄液に置換して前記微細管を洗浄するエッチング液洗浄工程と、
をさらに含むことを特徴とする、請求項１から請求項４のいずれかに記載の方法。 After the degreasing liquid cleaning step, an etching step of performing an etching process by replacing the cleaning liquid with an etching liquid while preventing air from entering at least the inner space of the cleaned micropipe,
An etching solution cleaning step of cleaning the microtube by replacing the etchant with a cleaning solution while preventing air from entering at least the inner space of the etched microtube;
The method according to claim 1, further comprising:
活性化された前記微細管の少なくとも前記内空間に空気が入らないようにしながら活性化液を洗浄液に置換して前記微細管を洗浄する活性化液洗浄工程と、
をさらに含むことを特徴とする、請求項５に記載の方法。 After the step of cleaning the microtube following the etching step, an activation step of performing an activation process by replacing the cleaning liquid with an activation liquid while preventing air from entering at least the inner space of the cleaned microtubule. When,
An activated liquid cleaning step of cleaning the microtube by replacing the activated liquid with a cleaning liquid while preventing air from entering at least the inner space of the activated microtube;
The method of claim 5, further comprising:
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