JP2006181525A - Micro device and method for treating inside surface thereof - Google Patents

Micro device and method for treating inside surface thereof Download PDF

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JP2006181525A
JP2006181525A JP2004379768A JP2004379768A JP2006181525A JP 2006181525 A JP2006181525 A JP 2006181525A JP 2004379768 A JP2004379768 A JP 2004379768A JP 2004379768 A JP2004379768 A JP 2004379768A JP 2006181525 A JP2006181525 A JP 2006181525A
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microchannel
plating
microdevice
electroless
layer
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Takeshi Tobisawa
猛 飛澤
Hitoshi Sekine
均 関根
Fumihiko Ishiyama
文彦 石山
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DIC Corp
DIC Technology Corp
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DIC Technology Corp
Dainippon Ink and Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To form a smooth plated layer on the surface of a micro flow passage. <P>SOLUTION: A plurality of micro flow passages 2 each having 1-1,000 μm width and height are arranged on a micro device 1. A nickel layer is formed by pressurizing/supplying an electroless nickel-plating liquid to a supply port 2a of each of micro flow passages 2. A fluorocarbon resin-containing nickel layer is formed on the nickel layer by pressuring/supplying an electroless fluorocarbon resin-containing nickel-plating liquid to the supply port 2a. Each of the nickel-plating liquids thus pressurized surmounts the surface tension of each of the nickel-plating liquids to be generated at the supply port of each of micro flow passages and intrudes into each of micro flow passages so that the surface of each of micro flow passages is brought into contact with each of the nickel-plating liquids and plated. As a result, the smooth plated layer being the fluorocarbon resin-containing nickel layer can be formed on the surface of each of micro flow passages and consequently a fluid can be made to flow smoothly without adhering to the surface of each of micro flow passages or blocking each of micro flow passages. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、極微細な寸法を有するマイクロ流路内に各種流体を流して化学反応や分析、晶析等を行うようにしたマイクロデバイス及びその内面処理方法に関する。   The present invention relates to a microdevice in which various fluids are allowed to flow in microchannels having extremely fine dimensions to perform chemical reaction, analysis, crystallization, and the like, and an inner surface treatment method thereof.

近年、幅と高さや内径が１μｍから数百μｍの断面形状を有する微細なマイクロ流路を複数有するマイクロデバイスを用いて、各種流体をマイクロ流路内に導入することによって化学反応や分析等を行う技術が提案されている。このような技術の１つとして例えば特許文献１に記載されたマイクロデバイスがある。
このマイクロデバイスは、導入流路から導入された２種の流体を微細なマイクロ流路に供給して混合し、更に分離して別々の流路から排出する構成を備えている。これらの流体中にはその目的に応じて種々の物質を含ませておき、マイクロ流路内で接触、混合させて化学反応させるようにしている。
このようなマイクロデバイスに設けられたマイクロ流路は、断面形状の幅や高さまたは内径が１μｍ〜１０００μｍ未満程度に設定されている。そして、粘着性物質や粉体の粒子等を溶解させた流体をマイクロ流路に流して取り扱うようにしている。
特開２００４−３０５９３８号公報 In recent years, chemical reactions and analyzes have been conducted by introducing various fluids into a microchannel using a microdevice having a plurality of microchannels having a cross-sectional shape with a width, height and inner diameter of 1 μm to several hundred μm. Techniques to do are proposed. As one of such techniques, there is a microdevice described in Patent Document 1, for example.
This micro device has a configuration in which two types of fluids introduced from an introduction channel are supplied to a fine micro channel, mixed, further separated, and discharged from separate channels. These fluids contain various substances according to their purposes, and are brought into contact with and mixed in the microchannel for chemical reaction.
The microchannel provided in such a microdevice has a cross-sectional width, height, or inner diameter set to about 1 μm to less than 1000 μm. Then, a fluid in which an adhesive substance, powder particles or the like are dissolved is caused to flow through the micro flow path for handling.
JP 2004-305938 A

ところで、マイクロデバイスには加工が容易なステンレス等の金属が用いられており、微細なマイクロ流路の表面は通常の酸洗いをした金属表面であるために非常に表面が粗く、そのために流体中に含まれる粘着性物質や粉体の粒子等が付着し易く流路の閉塞や圧力上昇を引き起こし易いという不具合があった。
ところが、上述したようなマイクロ流路の表面に流体中の粘着性物質や粒子等が付着しにくくしようとした場合、一般的な電気めっきや無電解めっき等のめっき処理方法によって表面にめっき層を形成することが考えられる。しかしながら、この場合、めっき液を満たしためっき浴槽中にマイクロデバイスを漬けてめっき処理するものであるから、微細なマイクロ流路の開口にめっき液の表面張力が生じて内部にめっき液が十分浸入しなかった。そのため、マイクロ流路の表面をめっき層で被覆形成することはできなかった。 By the way, metals such as stainless steel, which are easy to process, are used for the microdevice, and the surface of the fine microchannel is a rough surface because it is a metal surface that has been subjected to normal pickling. There is a problem that the adhesive substance and powder particles contained in the film are likely to adhere, and the flow path is likely to be blocked or the pressure is increased.
However, when it is difficult for the adhesive substance or particles in the fluid to adhere to the surface of the microchannel as described above, a plating layer is formed on the surface by a general plating method such as electroplating or electroless plating. It is conceivable to form. However, in this case, since the micro device is immersed in the plating bath filled with the plating solution and plating is performed, the surface tension of the plating solution is generated in the opening of the minute micro flow path, and the plating solution is sufficiently infiltrated inside. I didn't. Therefore, the surface of the microchannel cannot be formed with a plating layer.

本発明は、このような実情に鑑みて、マイクロ流路の表面に滑らかなめっき層を形成するようにしたマイクロデバイス及びその内面処理方法を提供することを目的とする。   In view of such circumstances, an object of the present invention is to provide a microdevice in which a smooth plating layer is formed on the surface of a microchannel and a method for treating the inner surface thereof.

本発明によるマイクロデバイスは、幅と高さまたは内径が１〜１０００μｍの断面を有するマイクロ流路を設けたマイクロデバイスにおいて、マイクロ流路の供給口と排出口に圧力差を持たせて無電解用めっき液を供給して表面にめっき層を形成したことを特徴とする。
本発明では、マイクロ流路内に供給口と排出口に圧力差を持たせて無電解用めっき液を供給することで、マイクロ流路内の供給口に生じる無電解用めっき液の表面張力に打ち勝って内部に浸入させて表面全体に接触させることができ、これによってめっき処理で滑らかなめっき層を形成することができる。そのため、流体をマイクロ流路に流しても粒子等が付着したり閉塞したりすることを防止して連続的に流体の処理を行える。
なお、めっき液をマイクロ流路内に供給する際、圧力差を生じさせるために供給口に供給するめっき液を加圧してもよいし排出口のめっき液を減圧してもよい。 The microdevice according to the present invention is a microdevice provided with a microchannel having a cross section having a width and height or an inner diameter of 1 to 1000 μm, and has a pressure difference between the supply port and the discharge port of the microchannel and is used for electroless A plating solution is supplied to form a plating layer on the surface.
In the present invention, the surface tension of the electroless plating solution generated at the supply port in the microchannel is reduced by supplying the electroless plating solution with a pressure difference between the supply port and the discharge port in the microchannel. It can be overcome and infiltrated into the interior to be brought into contact with the entire surface, whereby a smooth plating layer can be formed by plating. Therefore, even if the fluid flows through the microchannel, the fluid can be continuously processed by preventing particles and the like from adhering or blocking.
When supplying the plating solution into the micro flow path, the plating solution supplied to the supply port may be pressurized or the discharge port may be depressurized in order to generate a pressure difference.

本発明によるマイクロデバイスの内面処理方法によれば、幅と高さまたは内径が１〜１０００μｍの断面を有するマイクロ流路を設けたマイクロデバイスにおいて、マイクロ流路の供給口と排出口に圧力差を持たせて無電解用ニッケルめっき液または無電解用フッ素樹脂含有ニッケルめっき液を供給して無電解めっきすることで表面にニッケル層またはフッ素樹脂含有ニッケル層を形成するようにしたことを特徴とする。
本発明では、圧力差によって無電解用ニッケルめっき液または無電解用フッ素樹脂含有ニッケルめっき液をマイクロ流路内に浸入させて無電解めっきすることで表面にニッケル層またはフッ素樹脂含有ニッケル層からなる均一厚みで滑めらかなめっき層を形成できる。この場合、マイクロ流路の表面にニッケル層を形成すれば、酸洗いしただけの無垢のマイクロ流路よりも表面が滑らかであり、またフッ素樹脂含有ニッケル層を形成すれば、フッ素樹脂の層によって平滑性と撥水性と発油性が良くなり、マイクロ流路の表面が一層滑らかであり、流体の付着等を抑えて流れを良好にする。 According to the method for treating the inner surface of a microdevice according to the present invention, in a microdevice having a microchannel having a cross section with a width and height or an inner diameter of 1 to 1000 μm, a pressure difference is generated between the supply port and the discharge port of the microchannel. A nickel layer or a fluororesin-containing nickel layer is formed on the surface by supplying an electroless nickel plating solution or an electroless fluororesin-containing nickel plating solution and performing electroless plating. .
In the present invention, an electroless nickel plating solution or an electroless fluororesin-containing nickel plating solution is infiltrated into the microchannel by a pressure difference, and the surface is made of a nickel layer or a fluororesin-containing nickel layer. A smooth plating layer having a uniform thickness can be formed. In this case, if a nickel layer is formed on the surface of the microchannel, the surface is smoother than a pure microchannel that is simply pickled, and if a fluororesin-containing nickel layer is formed, Smoothness, water repellency, and oil repellency are improved, the surface of the microchannel is smoother, and adhesion of fluid is suppressed to improve flow.

本発明によるマイクロデバイスによれば、マイクロ流路の表面に滑らかなめっき層を形成することができて流体を流した場合に粘着性物質や流体中の粒子等が表面に付着したり流路を閉塞したりすることがなくスムーズに流れて連続的に処理でき、しかも洗浄時間の短縮を図ることができると共に流体の付着残留に起因する汚染や品質劣化を防止できる。
また、本発明によるマイクロデバイスの内面処理方法によれば、圧力差によって表面張力に打ち勝って無電解用ニッケルめっき液または無電解用フッ素樹脂含有ニッケルめっき液を微細なマイクロ流路内に浸入させて無電解めっきすることで表面にニッケル層またはフッ素樹脂含有ニッケル層からなる均一厚みで滑らかなめっき層を形成できる。 According to the microdevice of the present invention, a smooth plating layer can be formed on the surface of the microchannel, and when a fluid is flowed, adhesive substances or particles in the fluid adhere to the surface or the channel It can flow smoothly and can be continuously processed without being clogged, and the cleaning time can be shortened, and contamination and quality deterioration due to residual adhesion of fluid can be prevented.
Further, according to the method for treating the inner surface of the microdevice according to the present invention, the electroless nickel plating solution or the electroless fluororesin-containing nickel plating solution is allowed to enter the fine micro flow path by overcoming the surface tension due to the pressure difference. By performing electroless plating, a smooth plating layer having a uniform thickness composed of a nickel layer or a fluorine resin-containing nickel layer can be formed on the surface.

本発明によるマイクロデバイスでは、めっき層はニッケルまたはフッ素樹脂含有ニッケル層で形成されていることが好ましい。
ニッケル層またはフッ素樹脂含有ニッケル層によって滑らかで均一な厚みのめっき層を形成でき、そのために流体をマイクロ流路に流した際に表面に付着することを抑制でき、そのためにマイクロ流路が詰まったり圧力が上昇することを防止できて連続して流体を流して化学反応や分析、晶析等の処理を行える。 In the microdevice according to the present invention, the plating layer is preferably formed of nickel or a fluorine resin-containing nickel layer.
A smooth and uniform plating layer can be formed with a nickel layer or a fluororesin-containing nickel layer, which prevents the fluid from adhering to the surface when flowing into the microchannel, which can clog the microchannel It is possible to prevent the pressure from rising, and to conduct a chemical reaction, analysis, crystallization, etc. by continuously flowing a fluid.

本発明によるマイクロデバイスの内面処理方法では、無電解用ニッケルめっき液または無電解用フッ素樹脂含有ニッケルめっき溶液は、マイクロ流路の供給口と排出口での圧力差が０．２ＭＰａまたはそれ以下となるようにしてもよい。
これによってマイクロ流路の供給口に表面張力を生じさせることなく内部に無電解用ニッケルめっき液または無電解用フッ素樹脂含有ニッケルめっき液を浸入させて表面全体に接触させることができ、無電解めっきによって表面に均一厚みで滑らかなニッケル層またはフッ素樹脂含有ニッケル層を形成できる。
なお、マイクロ流路の表面に無電解用フッ素樹脂含有ニッケルめっきを施す前に、無電解めっきによるニッケル層を形成することが好ましい。ニッケル層はフッ素樹脂含有ニッケル層となじみがよく、表面にフッ素樹脂による層を形成できる。
この場合、ニッケル層はマイクロデバイスを製造する前のプレートに形成し、これら複数のプレートを積層して加圧することで拡散接合によって相互に固着してマイクロデバイスを製造することで、マイクロ流路の表面にニッケル層を形成してもよい。或いはマイクロデバイスの各マイクロ流路に供給口と排出口での圧力差を持たせて無電解用ニッケルめっき液を供給することで表面にニッケル層を形成してもよい。 In the microdevice inner surface treatment method according to the present invention, the electroless nickel plating solution or the electroless fluororesin-containing nickel plating solution has a pressure difference of 0.2 MPa or less between the supply port and the discharge port of the microchannel. It may be made to become.
As a result, the electroless nickel plating solution or the electroless fluororesin-containing nickel plating solution can be infiltrated and brought into contact with the entire surface without causing surface tension at the microchannel supply port. Thus, a smooth nickel layer or a fluororesin-containing nickel layer having a uniform thickness can be formed on the surface.
In addition, it is preferable to form a nickel layer by electroless plating before performing electroless fluororesin-containing nickel plating on the surface of the microchannel. The nickel layer is familiar with the fluororesin-containing nickel layer, and a layer of fluororesin can be formed on the surface.
In this case, the nickel layer is formed on the plate before manufacturing the microdevice, and the plurality of plates are stacked and pressed to adhere to each other by diffusion bonding to manufacture the microdevice. A nickel layer may be formed on the surface. Alternatively, a nickel layer may be formed on the surface by supplying an electroless nickel plating solution to each micro flow path of the microdevice with a pressure difference between the supply port and the discharge port.

以下、本発明の第一実施例によるマイクロデバイスの斜視図、図２はマイクロデバイスのプレートを示す分解斜視図、図３はマイクロ流路の断面図、図４はマイクロ流路の無電解めっき装置を示す図、図５はマイクロ流路のめっき方法のフローシートである。
図１及び図２に示す第一実施例によるマイクロデバイス１は、一方の面３ａに断面凹溝形状のマイクロ流路２′を所定間隔で複数配列形成してなるプレート３を互いに直交する向きで交互に積層したものである。各プレート３は例えばステンレス製等の金属製からなる例えば一辺が２０ｍｍをなす正方形板状であり、積層状態で互いに固着して構成されている。マイクロデバイス１の各マイクロ流路２は両端に開口するトンネル形状であり、縦断面が例えば長方形で幅６００μｍ、高さ３００μｍ、長さ２０ｍｍとされ、１枚のプレート３に例えば数本から数十本設けられている。 1 is a perspective view of a micro device according to a first embodiment of the present invention, FIG. 2 is an exploded perspective view showing a plate of the micro device, FIG. 3 is a cross-sectional view of the micro channel, and FIG. 4 is an electroless plating apparatus for the micro channel. FIG. 5 is a flow sheet of a microchannel plating method.
The microdevice 1 according to the first embodiment shown in FIGS. 1 and 2 has a plate 3 formed by arranging a plurality of microchannels 2 'having a concave groove shape on one surface 3a at a predetermined interval in a direction orthogonal to each other. Alternating layers are stacked. Each plate 3 is made of a metal such as stainless steel, for example, and has a square plate shape with a side of 20 mm, and is fixed to each other in a laminated state. Each microchannel 2 of the microdevice 1 has a tunnel shape that opens at both ends, has a vertical cross section of, for example, a rectangle, a width of 600 μm, a height of 300 μm, and a length of 20 mm. The book is provided.

図１に示すマイクロデバイス１は、一方の方向Ａのマイクロ流路２…には例えば流体としてカルナバワックス２０ｗｔ％をＭＥＫ（メチルエチルケトン）８０ｗｔ％に溶解したものを主液として加熱した状態で流す。Ａ方向に直交するＢ方向のマイクロ流路２…には例えば水等の冷媒の流体を流す。主液と冷媒を高さ方向にずらして互いに直交するマイクロ流路２…に流すことで主液は急冷され、溶解前よりも微細な結晶として析出する。この場合、例えばＭＥＫに溶解する前のカルナバワックスの粒子を平均粒径４０〜５０μｍとして、急冷して晶析することで平均粒径１０μｍ以下、例えば４〜５μｍ程度に小さくできる。
このようなマイクロデバイス１のマイクロ流路２の表面には２重のコーティング層として、図３に示すように薄いめっき層からなるニッケル層４と、更にその表面のフッ素樹脂含有ニッケル層５とが積層して形成されている。ニッケル層４とフッ素樹脂含有ニッケル層５は後述のように無電解めっきで形成され、マイクロ流路２の表面をコーティングするフッ素樹脂含有ニッケル層５はフッ素樹脂のために特に平滑で撥水性と発油性に優れ、主液や冷媒等の各種流体中に含まれる物質粒子や粘着性物質等が付着したりしない。 In the microdevice 1 shown in FIG. 1, a microfluidic channel 2 in one direction A is flowed in a heated state with, for example, 20 wt% of carnauba wax dissolved in 80 wt% of MEK (methyl ethyl ketone) as a fluid. A coolant fluid such as water is allowed to flow through the microchannels 2 in the B direction orthogonal to the A direction. The main liquid and the refrigerant are shifted in the height direction and are allowed to flow through the micro flow paths 2 orthogonal to each other, whereby the main liquid is rapidly cooled and deposited as fine crystals than before the dissolution. In this case, for example, the carnauba wax particles before being dissolved in MEK can be reduced to an average particle size of 10 μm or less, for example, about 4 to 5 μm by rapidly cooling and crystallization with an average particle size of 40 to 50 μm.
As shown in FIG. 3, a nickel layer 4 made of a thin plating layer as shown in FIG. 3 and a fluororesin-containing nickel layer 5 on the surface are formed on the surface of the microchannel 2 of the microdevice 1 as described above. It is formed by stacking. The nickel layer 4 and the fluororesin-containing nickel layer 5 are formed by electroless plating as described later, and the fluororesin-containing nickel layer 5 that coats the surface of the microchannel 2 is particularly smooth and water-repellent because of the fluororesin. It is excellent in oiliness and does not adhere to substance particles or sticky substances contained in various fluids such as main liquid and refrigerant.

次にマイクロ流路２のコーティング層形成方法即ち内面処理方法について図４及び図５により説明する。
図４に示す無電解めっき装置１０は、マイクロデバイス１の一方向の各マイクロ流路２内に供給する循環管路１１に、めっき液を貯留する貯留槽１２と、貯留槽１２から流出するめっき液を例えば９０℃程度に加熱する加熱器１３と、加熱されためっき液を圧力Ｐａに加圧してマイクロデバイス１の各マイクロ流路２の一方の開口である供給口２ａにコネクタ９を介して供給するポンプ１４とを備えている。各マイクロ流路２の他方の開口である排出口２ｂには狭窄部１５を設けて各供給口２ａに対して開口面積を小さく設定する。
そして、排出口２ｂにおけるマイクロデバイス１外のめっき液の圧力Ｐｂを供給口２ａのめっき液の圧力Ｐａより小さく設定する。圧力差（Ｐａ−Ｐｂ）は、例えば、０＜（Ｐａ−Ｐｂ）≦０．２ＭＰａ（メガパスカル）とする。マイクロ流路２の供給口２ａから排出口２ｂまでの空間を脱気して内部を確実にめっき液で満たすために脱気用のバルブ（図示せず）を設置しておく。 Next, a coating layer forming method of the microchannel 2, that is, an inner surface processing method will be described with reference to FIGS.
An electroless plating apparatus 10 shown in FIG. 4 has a storage tank 12 that stores a plating solution and a plating that flows out of the storage tank 12 in a circulation pipe 11 that is supplied into each microchannel 2 in one direction of the microdevice 1. For example, a heater 13 that heats the solution to about 90 ° C., and the heated plating solution is pressurized to a pressure Pa to the supply port 2 a that is one opening of each microchannel 2 of the microdevice 1 via the connector 9. And a pump 14 to be supplied. A narrowing portion 15 is provided in the discharge port 2b, which is the other opening of each microchannel 2, and the opening area is set small with respect to each supply port 2a.
Then, the pressure Pb of the plating solution outside the microdevice 1 at the discharge port 2b is set smaller than the pressure Pa of the plating solution at the supply port 2a. The pressure difference (Pa−Pb) is, for example, 0 <(Pa−Pb) ≦ 0.2 MPa (megapascal). A deaeration valve (not shown) is installed in order to deaerate the space from the supply port 2a to the discharge port 2b of the microchannel 2 and to reliably fill the interior with the plating solution.

次にマイクロデバイス１の各マイクロ流路２の表面にフッ素樹脂含有ニッケル層５を形成する内面処理方法について図５に沿って説明する。
先ず、前処理として、マイクロデバイス１の各マイクロ流路２内をエア抜きした状態でアルカリ溶液で脱脂処理をし（ステップ１０１）、その後、水洗いをする（ステップ１０２）。そして、マイクロ流路２の表面を塩酸等の酸によって表面活性化処理を施す（ステップ１０３）。次いで図４に示す装置１０と同様な無電解めっき装置を用いて、無電解用ニッケルめっき液を、各マイクロ流路２の供給口２ａで圧力Ｐａに加圧して排出口２ｂのめっき液圧力Ｐｂとの圧力差（Ｐａ−Ｐｂ）を設定した状態で供給して無電解めっきを施し、各マイクロ流路２の表面にニッケル層４を形成する（ステップ１０４）。
なお、無電解用ニッケルめっき液は、ニッケル陽イオンの原料として硫酸ニッケル、還元剤として次亜リン酸ソーダ、錯化剤として有機のある種のアルキルヒドロオキシカルボン酸、その他反応促進剤、安定剤等を主成分とする。また、エア抜き（脱気）はアルカリ溶液による脱脂処理段階だけでなく、塩酸、ニッケルめっき液等をマイクロ流路２の表面に接触させる各処理段階でも行う。 Next, an inner surface treatment method for forming the fluororesin-containing nickel layer 5 on the surface of each microchannel 2 of the microdevice 1 will be described with reference to FIG.
First, as a pretreatment, degreasing treatment is performed with an alkaline solution in a state where each microchannel 2 of the microdevice 1 is evacuated (step 101), and then washed with water (step 102). Then, the surface of the microchannel 2 is subjected to a surface activation treatment with an acid such as hydrochloric acid (step 103). Next, using an electroless plating apparatus similar to the apparatus 10 shown in FIG. 4, the electroless nickel plating solution is pressurized to the pressure Pa at the supply port 2a of each microchannel 2 and the plating solution pressure Pb at the discharge port 2b. And a pressure difference (Pa-Pb) is set and electroless plating is performed to form a nickel layer 4 on the surface of each microchannel 2 (step 104).
The electroless nickel plating solution is composed of nickel sulfate as a nickel cation raw material, sodium hypophosphite as a reducing agent, certain organic alkylhydroxycarboxylic acids as complexing agents, other reaction accelerators and stabilizers. Etc. as the main component. In addition, air bleeding (deaeration) is performed not only in a degreasing treatment step using an alkaline solution, but also in each treatment step in which hydrochloric acid, a nickel plating solution, or the like is brought into contact with the surface of the microchannel 2.

次に、マイクロデバイス１を上述した無電解めっき装置１０にセットしてニッケル層４の上にフッ素樹脂含有ニッケル層５を形成する（ステップ１０５）。無電解用フッ素樹脂含有ニッケルめっき液は、上述した無電解用ニッケルめっき液中にフッ素樹脂（「テフロン（登録商標）」：株式会社デュポン社製）の微細な粒子を分散させたものである。加熱器１３で加熱されためっき液をポンプ１４で圧力Ｐａに加圧した状態でマイクロデバイス１の各マイクロ流路２に供給口２ａから供給する。排出口２ｂの圧力Ｐｂ（＜Ｐａ）とのめっき液の圧力差は（Ｐａ−Ｐｂ）に設定される。
ここで、従来の無電解めっき方法ではマイクロデバイス１を単に浴槽内のめっき液に浸漬するだけであるために、各マイクロ流路２の供給口２ａと排出口２ｂで生じる表面張力によって内部にめっき液が浸透しない。これに対し、本実施例では、上述のように圧力差（Ｐａ−Ｐｂ）を印加し、しかも各マイクロ流路２内は脱気されているので、各マイクロ流路２の表面全体に無電解用フッ素樹脂含有ニッケルめっき液が接触する。このめっき液を加圧状態で微細な各マイクロ流路２に供給することで表面張力等が生じてもめっき液を各マイクロ流路２内に押し込んで表面全体を無電解めっきできる。そのため、めっき層として平滑で撥水性と発油性に優れたニッケルフッ素樹脂層５を形成できる。
そしてマイクロデバイス１の他方向のマイクロ流路２の内面処理についても同様に行う。 Next, the microdevice 1 is set in the electroless plating apparatus 10 described above, and the fluororesin-containing nickel layer 5 is formed on the nickel layer 4 (step 105). The electroless fluororesin-containing nickel plating solution is obtained by dispersing fine particles of a fluororesin (“Teflon (registered trademark)” manufactured by DuPont) in the above-described electroless nickel plating solution. The plating solution heated by the heater 13 is supplied from the supply port 2 a to each microchannel 2 of the microdevice 1 while being pressurized to the pressure Pa by the pump 14. The pressure difference of the plating solution with respect to the pressure Pb (<Pa) of the discharge port 2b is set to (Pa-Pb).
Here, in the conventional electroless plating method, since the microdevice 1 is simply immersed in the plating solution in the bathtub, the inside is plated by the surface tension generated at the supply port 2a and the discharge port 2b of each microchannel 2. The liquid does not penetrate. In contrast, in the present embodiment, the pressure difference (Pa−Pb) is applied as described above, and the inside of each microchannel 2 is deaerated. Fluorine resin-containing nickel plating solution for contact. By supplying this plating solution to each micro-channel 2 in a pressurized state, even if surface tension or the like occurs, the plating solution can be pushed into each micro-channel 2 to electrolessly plate the entire surface. Therefore, the nickel fluororesin layer 5 which is smooth and excellent in water repellency and oil repellency can be formed as the plating layer.
The inner surface treatment of the microchannel 2 in the other direction of the microdevice 1 is similarly performed.

上述のように本実施例による処理方法によれば、マイクロ流路２内に供給する無電解用フッ素樹脂含有ニッケルめっき液を加圧状態で供給することで、断面が例えば幅６００μｍ×高さ３００μｍ程度の極微細なマイクロ流路２であっても表面全体を全長に亘って確実に無電解めっきできる。
そして、得られたマイクロデバイス１は各マイクロ流路２の表面に無電解フッ素樹脂含有のニッケル層５が形成されているために平滑で撥水性と発油性に優れ、流体の付着や閉塞を防止できる。そのため、流体の付着等による圧力上昇を抑制して連続的に安定して微細結晶等の物質を生産したり反応させることができ、平滑な表面のために圧力低下させて安全運転できる。また、その後のマイクロ流路２内の洗浄時間を短縮でき、流体が付着残留することに起因する汚染や品質劣化を防止できる。そのため、腐食性流体や物質からマイクロデバイス１を保護できる。 As described above, according to the processing method of this embodiment, the electroless fluororesin-containing nickel plating solution supplied into the microchannel 2 is supplied in a pressurized state, so that the cross section is, for example, 600 μm wide × 300 μm high. Even if the microchannel 2 is extremely fine, the entire surface can be reliably electrolessly plated over the entire length.
And since the obtained microdevice 1 has the electroless fluororesin-containing nickel layer 5 formed on the surface of each microchannel 2, it is smooth and excellent in water repellency and oil repellency, and prevents adhesion and blockage of fluid. it can. For this reason, it is possible to suppress the pressure increase due to the adhesion of fluid and the like, and to continuously produce and react a substance such as fine crystals, and to reduce the pressure for a smooth surface, and to operate safely. Further, the subsequent cleaning time in the microchannel 2 can be shortened, and contamination and quality deterioration due to the fluid remaining attached can be prevented. Therefore, the microdevice 1 can be protected from corrosive fluids and substances.

次に本発明の第二実施例について図６及び図７に沿って説明する。
第二実施例によるマイクロデバイス１は、金属製の各プレート３の表面に無電解めっき（または電解めっき）によるニッケル層４が予め施されている（図６参照）。そのため、マイクロデバイス１の製造に際しては、複数のプレート３の表面を磨き上げて図１に示すように互いに直交する方向に交互に積層した状態で治具で把持して所定圧力をかけて固定し、適切な温度で加熱保持する。これによって各プレート３、３同士が拡散接合される（ステップ１１０）。
このようにして得られたマイクロデバイス１について、第一実施例と同様に前処理としてマイクロ流路２内をアルカリ溶液で脱脂処理をし（ステップ１１１）、その後、水洗いをする（ステップ１１２）。 Next, a second embodiment of the present invention will be described with reference to FIGS.
In the microdevice 1 according to the second embodiment, a nickel layer 4 by electroless plating (or electrolytic plating) is applied in advance to the surface of each metal plate 3 (see FIG. 6). Therefore, when manufacturing the microdevice 1, the surfaces of the plurality of plates 3 are polished and gripped with a jig in a state of being alternately stacked in directions orthogonal to each other as shown in FIG. Hold heated at an appropriate temperature. Thus, the plates 3 and 3 are diffusion bonded (step 110).
The micro device 1 thus obtained is degreased with an alkaline solution as a pretreatment in the same manner as in the first embodiment (step 111), and then washed with water (step 112).

次に、マイクロデバイス１を第一実施例と同様に圧力Ｐａに加圧した無電解用フッ素樹脂含有ニッケルめっき液を各マイクロ流路２内に供給してニッケル層４の上にフッ素樹脂含有ニッケル層５を無電解めっきで形成する（ステップ１１３）。
このようにして第一実施例と同様にマイクロ流路２の表面全体に平滑で撥水性と発油性に優れたフッ素樹脂含有ニッケル層５を形成でき、各種流体を流した時に流体中の粒子等の付着を防止できて圧力上昇を防止できる等、同様の効果を得られる。
なお、本実施例において、プレート３を拡散接合した後、各マイクロ流路２を酸洗いして再び無電解用ニッケルめっきを行ってニッケル層４を形成し、次に無電解用フッ素樹脂含有ニッケルめっきを行ってフッ素樹脂含有ニッケル層５を形成してもよい。 Next, an electroless fluororesin-containing nickel plating solution in which the microdevice 1 is pressurized to the pressure Pa in the same manner as in the first embodiment is supplied into each microchannel 2 and the fluororesin-containing nickel is deposited on the nickel layer 4. Layer 5 is formed by electroless plating (step 113).
In this manner, the fluororesin-containing nickel layer 5 that is smooth and excellent in water repellency and oil repellency can be formed on the entire surface of the microchannel 2 as in the first embodiment. The same effect can be obtained, for example, that the adhesion of water can be prevented and the pressure rise can be prevented.
In this embodiment, after the plate 3 is diffusion bonded, each microchannel 2 is pickled and subjected to electroless nickel plating again to form the nickel layer 4, and then the electroless fluororesin-containing nickel The fluororesin-containing nickel layer 5 may be formed by plating.

また、第三実施例として、無電解用フッ素樹脂含有ニッケル層５をめっき形成をすることなく、無電解用ニッケルめっきによって各マイクロ流路２の表面にニッケル層４を形成して内面処理を終了するようにしてもよい。この内面処理工程は第一実施例におけるステップ１０１〜１０４と同様である。
この場合、第一及び第二実施例のようにマイクロ流路２の表面に無電解用フッ素樹脂含有ニッケル層５を形成した場合よりも効果は落ちるが、マイクロデバイス１の各マイクロ流路２を酸洗いしただけの従来のものよりも平滑性がよく、流体の付着や閉塞を防止できる等という第一及び第二実施例と同様の効果を得られる。 As a third embodiment, the inner surface treatment is completed by forming the nickel layer 4 on the surface of each microchannel 2 by electroless nickel plating without plating the electroless fluororesin-containing nickel layer 5. You may make it do. This inner surface treatment process is the same as steps 101 to 104 in the first embodiment.
In this case, although the effect is lower than when the electroless fluororesin-containing nickel layer 5 is formed on the surface of the microchannel 2 as in the first and second embodiments, each microchannel 2 of the microdevice 1 is The same effects as those of the first and second embodiments can be obtained in that the smoothness is better than that of the conventional one just pickled and the adhesion and blockage of fluid can be prevented.

次に本発明のマイクロデバイス１のマイクロ流路２の内面処理方法の具体例について実施例１、２として説明する。
（実施例１）
実施例１は第一実施例に沿った内面処理方法であり、図５のフローシートに沿って説明する。
マイクロデバイス１のマイクロ流路２は断面が幅６００μｍ、高さ３００μｍの長方形であり、プレート３に沿って長さ４０ｍｍに亘って延びて両端に開口している。マイクロデバイス１は積層状態でマイクロ流路２を１９２本設けているステンレス製（ＳＵＳ３０４）である。なお、マイクロ流路２内は各工程毎に脱気するものとする。
このマイクロデバイス１にチューブポンプを接続してマイクロ流路２内に温度６０℃のアルカリ溶液を供給して５分間脱脂処理した（ステップ１０１）。その後、室温下で水洗いを２分間行った（ステップ１０２）。次に室温下で塩酸をマイクロ流路２内に供給して３分間表面活性化処理を施した（ステップ１０３）。そして約９０℃の無電解用ニッケルめっき液をマイクロ流路２内に供給して約１０分間めっき処理した（ステップ１０４）。このときのマイクロ流路２の供給口２ａと排出口２ｂのめっき液の圧力差が０．２ＭＰａとなるようにコントロールした。
そして約９０℃の無電解用フッ素樹脂含有ニッケルめっき液をマイクロ流路２内に約１００ｍｌ／ｍｉｎの流量で供給して約２０分間めっき処理した（ステップ１０５）。このときのマイクロ流路２の供給口２ａと排出口２ｂのめっき液の圧力差が０．２ＭＰａとなるようにコントロールした。 Next, specific examples of the method for treating the inner surface of the microchannel 2 of the microdevice 1 of the present invention will be described as Examples 1 and 2.
Example 1
Example 1 is an inner surface treatment method according to the first example, and will be described along the flow sheet of FIG.
The microchannel 2 of the microdevice 1 has a rectangular cross section having a width of 600 μm and a height of 300 μm, and extends along the plate 3 over a length of 40 mm and opens at both ends. The microdevice 1 is made of stainless steel (SUS304) provided with 192 microchannels 2 in a stacked state. In addition, the inside of the microchannel 2 shall be deaerated for every process.
A tube pump was connected to the microdevice 1 and an alkaline solution having a temperature of 60 ° C. was supplied into the microchannel 2 to degrease it for 5 minutes (step 101). Thereafter, washing with water was performed at room temperature for 2 minutes (step 102). Next, hydrochloric acid was supplied into the microchannel 2 at room temperature, and surface activation treatment was performed for 3 minutes (step 103). Then, an electroless nickel plating solution at about 90 ° C. was supplied into the microchannel 2 and plated for about 10 minutes (step 104). At this time, the pressure difference between the plating solution at the supply port 2a and the discharge port 2b of the microchannel 2 was controlled to be 0.2 MPa.
Then, an electroless fluororesin-containing nickel plating solution at about 90 ° C. was supplied into the microchannel 2 at a flow rate of about 100 ml / min and plated for about 20 minutes (step 105). At this time, the pressure difference between the plating solution at the supply port 2a and the discharge port 2b of the microchannel 2 was controlled to be 0.2 MPa.

内面処理の終了後、マイクロデバイス１を切断して数カ所のマイクロ流路２の断面を観察したところ、フッ素樹脂含有ニッケル層５が表面に均一厚みに析出してコーティングされていた。
そして、このマイクロデバイス１を用いて８０ｗｔ％ＭＥＫに溶解した２０ｗｔ％カルナバワックス溶液を主液としてＡ方向のマイクロ流路２に流し、冷却水からなる冷媒をＢ方向にマイクロ流路２に供給して急冷させてカルナバワックスを析出する実験を行ったところ、流路２が閉塞されることもなく、無電解用めっき層４，５をコーティングする前の表面無処理状態の従来のマイクロ流路より安定的に長時間の連続運転ができた。 After completion of the inner surface treatment, the microdevice 1 was cut and the cross sections of several microchannels 2 were observed. As a result, the fluororesin-containing nickel layer 5 was deposited on the surface with a uniform thickness and coated.
Then, using this microdevice 1, a 20 wt% carnauba wax solution dissolved in 80 wt% MEK is flowed to the micro flow path 2 in the A direction as a main liquid, and a coolant composed of cooling water is supplied to the micro flow path 2 in the B direction. In an experiment in which carnauba wax was precipitated by rapid cooling, the flow path 2 was not clogged, and compared with the conventional micro flow path in a non-surface-treated state before coating the electroless plating layers 4 and 5. Stable and continuous operation was possible for a long time.

（実施例２）
実施例２による内面処理方法について、図７のフローシートに沿って説明する。
マイクロデバイス１のマイクロ流路２は断面が幅６００μｍ、高さ３００μｍの長方形であり、長さ４０ｍｍで両端に開口している。マイクロデバイス１は積層状態でマイクロ流路２を１９２本設けているステンレス製（ＳＵＳ３０４）である。しかも、本実施例２では各プレート３の段階で予め表面に無電解用ニッケルめっき処理によってニッケル層４が形成され、これらプレート３…を積層して拡散接合によってマイクロデバイス１を製造した（ステップ１１０）。各工程毎にマイクロ流路２内を脱気する。
このマイクロデバイス１にチューブポンプを接続してマイクロ流路２内に温度６０℃のアルカリ溶液を供給して５分間脱脂処理した（ステップ１１１）。その後、室温下で水洗いを２分間行った（ステップ１１２）。
そして約９０℃の無電解用フッ素樹脂含有ニッケルめっき液をマイクロ流路２内に約１００ｍｌ／ｍｉｎの流量で供給して約２０分間めっき処理した（ステップ１０３）。このときのマイクロ流路２の供給口２ａと排出口２ｂのめっき液の圧力差が０．２ＭＰａとなるようにコントロールした。 (Example 2)
The inner surface processing method according to the second embodiment will be described along the flow sheet of FIG.
The microchannel 2 of the microdevice 1 is a rectangle having a width of 600 μm and a height of 300 μm, and has a length of 40 mm and is open at both ends. The microdevice 1 is made of stainless steel (SUS304) provided with 192 microchannels 2 in a stacked state. In addition, in Example 2, the nickel layer 4 is formed on the surface in advance by the electroless nickel plating process at the stage of each plate 3, and these plates 3 are stacked to manufacture the microdevice 1 by diffusion bonding (step 110). ). The inside of the microchannel 2 is deaerated for each step.
A tube pump was connected to the microdevice 1 and an alkaline solution having a temperature of 60 ° C. was supplied into the microchannel 2 for degreasing treatment for 5 minutes (step 111). Thereafter, washing with water was performed at room temperature for 2 minutes (step 112).
Then, an electroless fluororesin-containing nickel plating solution at about 90 ° C. was supplied into the microchannel 2 at a flow rate of about 100 ml / min for about 20 minutes (step 103). At this time, the pressure difference between the plating solution at the supply port 2a and the discharge port 2b of the microchannel 2 was controlled to be 0.2 MPa.

内面処理の終了後、マイクロデバイス１を切断して数カ所のマイクロ流路２の断面を観察したところ、フッ素樹脂含有ニッケル層５が内表面に均一厚みに析出してめっき形成されていた。本実施例２では、ニッケルめっき工程が省略されているために実施例１と比較して施行時間が短く、コストが低廉になる。   After completion of the inner surface treatment, the microdevice 1 was cut and the cross sections of several microchannels 2 were observed. As a result, the fluororesin-containing nickel layer 5 was deposited on the inner surface to have a uniform thickness. In the second embodiment, since the nickel plating step is omitted, the enforcement time is shorter and the cost is lower than that in the first embodiment.

なお、無電解用フッ素樹脂含有ニッケルめっき処理や無電解用ニッケルめっき処理等の各処理を行う場合、マイクロ流路２を上下方向に向けてめっき液等を下方から上方に注入すると、マイクロ流路２内のエアが一層抜け易い。また、マイクロ流路２内のめっき処理に際して供給口２ａで加圧することで排出口２ｂとの圧力差を設けることとしたが、これに代えて、またはこれに加えて排出口２ｂ側で吸引することで圧力差を設けてもよい。   In addition, when performing each process such as electroless fluororesin-containing nickel plating process or electroless nickel plating process, when the plating solution or the like is injected upward from below with the microchannel 2 directed upward, the microchannel Air in 2 is easier to escape. In addition, a pressure difference from the discharge port 2b is provided by applying pressure at the supply port 2a during the plating process in the microchannel 2, but instead of this, or in addition to this, suction is performed on the discharge port 2b side. A pressure difference may be provided.

また、マイクロ流路表面のめっき処理に際して排出口２ｂに狭窄部１５を設けることとしたが、狭窄部１５は必ずしも設けなくてもよく、マイクロ流路２の排出口２ｂ側より供給口２ａ側のめっき液の圧力が高く設定されていればよい。圧力差（Ｐａ−Ｐｂ）も０＜（Ｐａ−Ｐｂ）≦０．２ＭＰａであることが好ましいが、この範囲を超えても良く、要するにめっき液が微細なマイクロ流路２の供給口２ａ近傍で生じる表面張力にうち勝って内部に浸入して全面に接触する程度の圧力差（Ｐａ−Ｐｂ）があればよい。
また、上述の各実施例ではマイクロ流路２の流路縦断面を幅、高さがそれぞれ１μｍ〜１０００μｍの長方形に形成したが、マイクロ流路２の流路縦断面の形状は任意であり、例えば円形や正方形等でもよい。この場合でも内径や幅等の各寸法は１μｍ〜１０００μｍの範囲に設定するのが好ましい。 In addition, the narrowed portion 15 is provided in the discharge port 2b during the plating process on the surface of the microchannel. It is sufficient that the pressure of the plating solution is set high. The pressure difference (Pa−Pb) is also preferably 0 <(Pa−Pb) ≦ 0.2 MPa, but may exceed this range. In short, in the vicinity of the supply port 2a of the microchannel 2 where the plating solution is fine. There should be a pressure difference (Pa-Pb) that overcomes the surface tension that occurs and enters the inside and contacts the entire surface.
In each of the above-described embodiments, the channel longitudinal section of the microchannel 2 is formed into a rectangle having a width and height of 1 μm to 1000 μm, respectively, but the shape of the channel longitudinal section of the microchannel 2 is arbitrary, For example, it may be circular or square. Even in this case, the dimensions such as the inner diameter and the width are preferably set in the range of 1 μm to 1000 μm.

本発明の第一実施例によるマイクロデバイスの斜視図である。1 is a perspective view of a microdevice according to a first embodiment of the present invention. 図１に示すマイクロデバイスの一部のプレートを示す分解斜視図である。It is a disassembled perspective view which shows the one part plate of the microdevice shown in FIG. 図１に示すマイクロデバイスのマイクロ流路の縦断面図である。It is a longitudinal cross-sectional view of the microchannel of the microdevice shown in FIG. 内面処理工程におけるフッ素樹脂含有ニッケル層形成用の無電解めっき装置の概略構成を示す図である。It is a figure which shows schematic structure of the electroless-plating apparatus for fluororesin containing nickel layer formation in an inner surface treatment process. マイクロ流路表面のめっき処理工程を示すフローシート図である。It is a flow sheet figure which shows the plating process process of the microchannel surface. 第二実施例によるマイクロデバイスにおけるマイクロ流路の縦断面図である。It is a longitudinal cross-sectional view of the microchannel in the microdevice by a 2nd Example. マイクロ流路表面のめっき処理工程を示すフローシート図である。It is a flow sheet figure which shows the plating process process of the microchannel surface.

符号の説明Explanation of symbols

１ マイクロデバイス
２ マイクロ流路
２ａ 供給口
２ｂ 排出口
３ プレート
４ ニッケル層
５ フッ素樹脂含有ニッケル層
１４ ポンプ 1 Micro device 2 Micro flow path 2a Supply port 2b Discharge port 3 Plate 4 Nickel layer 5 Fluorine resin-containing nickel layer 14 Pump

Claims (3)

幅と高さまたは内径が１〜１０００μｍの断面を有するマイクロ流路を設けたマイクロデバイスにおいて、前記マイクロ流路の供給口と排出口に圧力差を持たせて無電解用めっき液を供給して表面にめっき層を形成したことを特徴とするマイクロデバイス。   In a microdevice provided with a microchannel having a cross section with a width and height or an inner diameter of 1 to 1000 μm, an electroless plating solution is supplied with a pressure difference between the supply port and the discharge port of the microchannel. A microdevice having a plating layer formed on a surface thereof. 前記めっき層はニッケル層またはフッ素樹脂含有ニッケル層で形成されている請求項１に記載のマイクロデバイス。   The micro device according to claim 1, wherein the plating layer is formed of a nickel layer or a fluorine resin-containing nickel layer. 幅と高さまたは内径が１〜１０００μｍの断面を有するマイクロ流路を設けたマイクロデバイスにおいて、前記マイクロ流路の供給口と排出口に圧力差を持たせて無電解用ニッケルめっき液または無電解用フッ素樹脂含有ニッケルめっき液を供給して無電解めっきすることで表面にニッケル層またはフッ素樹脂含有ニッケル層を形成するようにしたことを特徴とするマイクロデバイスの内面処理方法。

In a microdevice provided with a microchannel having a cross section with a width and height or an inner diameter of 1 to 1000 μm, a pressure difference is provided between the supply port and the discharge port of the microchannel and the electroless nickel plating solution or electroless A method for treating the inner surface of a microdevice, characterized in that a nickel layer or a fluororesin-containing nickel layer is formed on the surface by supplying a fluororesin-containing nickel plating solution for electroless plating.

JP2004379768A 2004-12-28 2004-12-28 Micro device and method for treating inside surface thereof Pending JP2006181525A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010527293A (en) * 2007-02-28 2010-08-12 コーニング インコーポレイテッド Method for making a microfluidic device
JP2016084831A (en) * 2014-10-23 2016-05-19 昭和電工株式会社 High-pressure gas container and manufacturing method thereof
KR20200090765A (en) 2017-12-05 2020-07-29 다이요 닛산 가부시키가이샤 Flow type reaction device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002037918A (en) * 2000-05-19 2002-02-06 Mitsubishi Heavy Ind Ltd Apparatus for recovering waste material derived from polystyrene and recovering method
JP2003062797A (en) * 2001-08-23 2003-03-05 Tosoh Corp Micro flow path structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002037918A (en) * 2000-05-19 2002-02-06 Mitsubishi Heavy Ind Ltd Apparatus for recovering waste material derived from polystyrene and recovering method
JP2003062797A (en) * 2001-08-23 2003-03-05 Tosoh Corp Micro flow path structure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010527293A (en) * 2007-02-28 2010-08-12 コーニング インコーポレイテッド Method for making a microfluidic device
JP2016084831A (en) * 2014-10-23 2016-05-19 昭和電工株式会社 High-pressure gas container and manufacturing method thereof
KR20200090765A (en) 2017-12-05 2020-07-29 다이요 닛산 가부시키가이샤 Flow type reaction device

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