WO2020013344A1 - Metal capillary provided in end portion with water-repellent outer circumferential surface - Google Patents

Metal capillary provided in end portion with water-repellent outer circumferential surface Download PDF

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Publication number
WO2020013344A1
WO2020013344A1 PCT/JP2019/027871 JP2019027871W WO2020013344A1 WO 2020013344 A1 WO2020013344 A1 WO 2020013344A1 JP 2019027871 W JP2019027871 W JP 2019027871W WO 2020013344 A1 WO2020013344 A1 WO 2020013344A1
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Prior art keywords
metal plating
outer peripheral
layer
film layer
plating
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PCT/JP2019/027871
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French (fr)
Japanese (ja)
Inventor
宮原　鐘一
伸也 田光
昌宏 仲山
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仲山貴金属鍍金株式会社
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Priority to JP2020530292A priority Critical patent/JPWO2020013344A1/en
Publication of WO2020013344A1 publication Critical patent/WO2020013344A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/02—Tubes; Rings; Hollow bodies
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals

Definitions

  • the present invention relates to a thin metal tube having a water-repellent outer peripheral surface on at least one end.
  • Patent Literature 1 discloses an electroformed tube useful as an extremely fine tube for accommodating a contact probe used for inspection of a semiconductor pattern necessary for manufacturing an integrated circuit such as an LSI, and a metal conductive layer provided on an outer peripheral surface by electrolytic plating. A method is disclosed in which an electrodeposit or the like is further formed around the thin stainless steel wire by electroforming, and then the stainless thin wire is pulled out and removed while leaving the metal conductive layer. ing.
  • This Patent Document 1 further suggests that the above-described electroformed tube can be used in the fields of biotechnology and medicine other than the semiconductor industry.
  • Patent Document 2 discloses a method of manufacturing a metal thin tube in which aggregation due to electrification is difficult to occur.
  • This metal thin tube forms a tubular noble metal plating layer by performing a noble metal plating process around a core material, and then forms a core. It is described that it can be produced by a method of removing material.
  • Patent Document 2 describes a tubular member for accommodating an X-ray opaque marker of a medical catheter, a pin or a spring of a contact probe for inspection of a semiconductor manufacturing apparatus, as an example of the use of a thin metal tube obtained by the above-described manufacturing method. ing.
  • Patent Literature 3 discloses a method of coating a metal article so as to have a superhydrophobic surface, wherein a coating layer coated with another metal on the surface of the metal article using a method such as a spontaneous oxidation-reduction reaction. It describes a method of forming and then contacting the surface of the metallization layer with a hydrophobic material such as thiol, nitrile or the like.
  • Patent Document 3 discloses, as examples of metal articles on which a superhydrophobic surface is formed, nails, buckets, forks, rods, metal beams, metal cables, rails, heat transfer sheets for heat exchangers, separators, filters, and the like. Examples of biomedical applications include stents, catheters, wound dressings, hollow tubes or tubes, sampling systems, and the like.
  • Patent No. 3888989 (Date of issue: March 7, 2007) JP-A-2017-125224 Japanese Patent No. 5581051 (Date of issue: August 27, 2014)
  • micropipette or microsyringe to collect test samples such as trace amounts of body fluids (blood, serum, etc.)
  • body fluids blood, serum, etc.
  • Techniques for injecting chemicals and the like have been developed, but in recent years, with the development of medical technology and inspection technology, micropipette and microsyringe with even better use and operability and improved quantitativeness. Development is required.
  • a liquid sampling device or a liquid discharging device used for medical or chemical tests such as micropipette or microsyringe
  • quantitative and quick collection and drainage operations of blood and sample liquid are required.
  • a major cause that hinders the realization of the sampling operation and the discharging operation in a quantitative and rapid manner is the high hydrophilicity of the tip of a micropipette or a microsyringe.
  • a micropipette or a microsyringe is manufactured using a metal or glass material such as stainless steel so that a sample solution can be collected with high quantitativeness, but the surface of a normal metal or glass material is high. Because of its hydrophilicity, the collected or discharged sample liquid wraps around the outer peripheral surface of the outer end of the micropipette or microsyringe that comes into contact with the sample liquid, which reduces the quantitativeness of the collected and discharged sample liquid. There is a problem that it is easy.
  • an object of the present invention is to provide a metal thin tube that can be suitably used as a micropipette, a microsyringe, or the like, and that has a high water repellency in a peripheral region at a distal end portion of an outer peripheral surface thereof. It is in.
  • the inventor of the present invention manufactures an electroformed tube having a new configuration by utilizing the technology developed from the electroformed tube manufacturing technology described in Patent Document 1 or Patent Document 2, and manufactures the electroformed tube.
  • manufactures the electroformed tube By subjecting at least a part of the surface of the tube (particularly, a region around the distal end portion of the outer peripheral surface) to high water repellency treatment, a region around the distal end portion of the outer peripheral surface that can be suitably used as a micropipette, a micro syringe, or the like.
  • a thin metal tube exhibiting excellent water repellency can be produced, and arrived at the present invention.
  • the fact that the inventor based on the present invention has newly found out is, firstly, that plating usually used for imparting a smooth decorative property or a functional surface to a metal molding or a resin molding.
  • plating usually used for imparting a smooth decorative property or a functional surface to a metal molding or a resin molding.
  • By performing the treatment on the outer peripheral surface of the core material formed of a metal material or a synthetic resin material intentionally, by selecting conditions that can obtain a non-smooth surface, countless projections are formed on the surface.
  • This is a fact that a cylindrical plating layer having a roughened surface (rough surface) is formed with good reproducibility.
  • the rough surface of the cylindrical plating surface is subjected to a surface property modification treatment for improving the water repellency of the surface typified by a formation treatment of a self-assembled monolayer (SAM). It is a fact that a cylindrical body having an outer peripheral surface exhibiting high water repellency can be obtained.
  • SAM self-assembled monolayer
  • the inventor of the present invention continued his research, and after forming a thin film layer (preferably having a smooth surface) of a noble metal such as gold on the surface (peripheral surface) of an extremely fine core material by using a plating process, A thick plating layer of a base metal such as nickel is formed on the surface of the noble metal plating thin film layer, and then a composite of the thus formed noble metal plating thin film layer and the thick plating layer of the base metal is separated from the core material. After obtaining a cylindrical plating composite, a base metal plating thin film layer having a rough surface with irregularities on the outer peripheral surface is formed on the outer peripheral surface of the cylindrical plating composite, and further, a base metal plating thin film layer is formed.
  • the outer peripheral region near the end on the side where water repellency is required (the region on the outer peripheral side of the rough surface having irregularities of the base metal plating thin film layer) ) Is a self-assembled monolayer (SAM)
  • SAM self-assembled monolayer
  • the inventors of the present invention based on the above new findings, as a result of further research, can be produced by the above method, the outer peripheral surface of the region near at least one end shows excellent water repellency, For example, they have succeeded in manufacturing a metal thin tube that can be advantageously used as a micropipette or a microsyringe.
  • the present invention resides in a thin metal tube having a water-repellent outer peripheral surface described below.
  • a first tubular noble metal plating layer, a tubular base metal plating layer in which a rough surface having irregularities is formed on an outer peripheral surface in a region near at least one end, and a rough surface of the above tubular base metal plating layer Is a metal thin tube including a second tubular noble metal plating layer having a rough surface with irregularities on the outer peripheral surface of the region where is formed, the outer peripheral surface of the rough surface with irregularities of the second tubular noble metal plating layer
  • Preferred embodiments of the above-described metal thin tube having a water-repellent outer peripheral surface in the region near the end according to the present invention are as follows.
  • the above-mentioned tubular base metal plating layer has a tubular base metal plating thick film layer on the inner peripheral side and a rough surface having irregularities on the outer peripheral surface in a region near at least one end formed on the outer peripheral side. Including a base metal plating thin film layer.
  • the water-repellent self-assembled monomolecular film is formed so as to cover the end surface of the tubular base metal plating layer which is in contact with the vicinity of the region where the roughened surface having irregularities is formed.
  • the water-repellent self-assembled monomolecular film has an end surface near the region where the rough surface having irregularities of the tubular base metal plating layer is formed, and the inner peripheral surface of the first tubular noble metal plating layer following the end surface. Is formed so as to cover at least a part of.
  • the first tubular noble metal plating layer is a gold plating layer.
  • the tubular base metal plating layer is a nickel plating layer.
  • a metal capillary micropipette or microsyringe provided with a water-repellent outer peripheral surface in a region near the end.
  • a thin metal tube having a water-repellent outer peripheral surface in the vicinity of the end can be easily manufactured by using the following method.
  • the thickness (average layer thickness) of each of the first tubular noble metal plating thin film layer and the second tubular noble metal plating thin film layer is preferably in the range of 0.01 to 1 ⁇ m.
  • the thickness of the base metal plating thick film layer formed on the surface is preferably in the range of 5 to 500 ⁇ m.
  • the base metal plating thin film layer having an uneven surface formed on the outer peripheral surface of the base metal plating thick film layer is a plating layer having a smaller thickness than the base metal plating thick film layer, and has a thickness of 1 to 50 ⁇ m. It is preferably within the range.
  • the layer thickness of the base metal plating thin film layer having an uneven surface means an average distance (average height) from the bottom surface to the average height of the uneven surface of the base metal plating thin film layer.
  • plat means “electroplating” unless otherwise specified.
  • the metal thin tube provided with a water-repellent outer peripheral surface on at least one end of the present invention is a region where a water-repellent self-assembled monomolecular film is formed (that is, an end of the thin tube or a region in the vicinity thereof, for example, High water repellency at the outer peripheral surface and the inner peripheral surface in contact with the end portion). Therefore, it is extremely useful as a micropipette, a microsyringe, or the like for collecting or injecting a sample with high quantitativeness.
  • FIG. 2 is a cross-sectional view of a metal thin tube having a water-repellent outer peripheral surface on at least one end of the present invention, showing a stacked structure of a plurality of plating films and a self-assembled monomolecular film constituting the metal thin tube. It is. An enlarged view (schematic view) is also attached.
  • a metal thin tube 1 having a water-repellent outer peripheral surface has a first noble metal plating thin film layer 2, a base metal plating thick film layer 3, and a base metal plating thin film layer having irregularities formed on the surface from the innermost peripheral side. 4, a second noble metal plated thin film layer 5 and a self-assembled monolayer 6.
  • FIG. 4 shows a high-speed photograph of a state in which a thin metal tube having a water-repellent outer peripheral surface of the present invention is vertically arranged, water is supplied to an upper end portion, and a state immediately before a water drop falls from a lower end portion.
  • photographed the state just before water was supplied from the lower end part and water was supplied to the upper end part is shown.
  • a noble metal plated thin film layer (first noble metal plated thin film layer) is formed around a linear material used as a core material by using an electroplating method.
  • a base metal plating thick film layer (a rough surface having irregularities may be formed on the surface) in order to obtain a plating composite, and then pulling out a core material from the plating layer composite, or
  • the cylindrical plating composite is separated by an operation such as dissolution removal.
  • a base metal plating thin film layer having a rough surface having irregularities on its surface is formed in at least a region near one end of the cylindrical plating composite, and then a precious metal is formed on the outer peripheral surface of the base metal plating thin film layer again.
  • a plating thin film layer (second noble metal plating thin film layer) is formed.
  • the second noble metal plating thin film layer formed in this manner inevitably becomes a rough surface having irregularities on the outer peripheral side of the rough surface having irregularities of the base metal plating thin film layer.
  • a water-repellent self-assembled monolayer is laminated on the surface of the second noble metal plating thin film layer.
  • examples of the core material used include a core material made of a metal such as stainless steel and a core material obtained by forming a synthetic resin such as a polyamide resin into a linear shape.
  • a core material made of a metal such as stainless steel
  • a core material obtained by forming a synthetic resin such as a polyamide resin into a linear shape.
  • the noble metal material used for forming the noble metal plating thin film layer is not particularly limited, and examples thereof include gold (Au), platinum (Pt), One or more noble metals selected from the group consisting of silver (Ag) and palladium (Pd), in particular, gold can be mentioned.
  • an alloy containing a noble metal such as gold as a main component and another noble metal or a base metal as a small component such as Au-Fe, Au-W, Au-Co, Au-Ni, or Au-Ag can also be used.
  • the thickness (average layer thickness) of the noble metal plating thin film layer (first noble metal plating thin film layer) formed on the outer peripheral surface of the core material is preferably in the range of 0.01 to 1 ⁇ m.
  • a base metal plating thick film layer (a plating thick film layer having a smooth surface) may be provided.
  • a thick base metal plating layer having a rough surface This base metal plating thick film layer can be obtained by using a known method for forming a base metal plating layer.
  • the base metal material that can be used for forming the base metal plating layer include nickel (Ni), an alloy of nickel and iron (Ni-Fe), an alloy of nickel and tungsten (Ni-W), and an alloy of nickel and cobalt (Ni-W). Co) and an alloy of nickel and manganese (Ni—Mn).
  • the thickness of the base metal plating thick film layer is preferably in the range of 20 to 500 ⁇ m.
  • the noble metal plating thin film layer (first noble metal plating thin film layer) formed on the outer peripheral surface of the core material and the base metal plating thick film layer formed on the outer peripheral surface of the noble metal plating thin film layer
  • a composite plating cylinder comprising a noble metal plating thin film layer and a base metal plating thick film layer formed on the outer peripheral surface of the noble metal plating thin film layer ( Tubular body) is obtained.
  • a base metal plated thin film layer (layer thickness is generally 0.5 to 20 ⁇ m) having the provided uneven surface (rough surface) is formed.
  • the base metal plating thin film layer on which the uneven surface with clear projections is formed on the surface can be obtained by using conditions different from those conventionally used for forming a base metal plating layer. . Note that such conditions vary depending on the composition of the plating solution and various plating operation conditions, and thus cannot be unconditionally determined. Those skilled in the art can easily determine the conditions by referring to the examples described in the present specification, changing the processing conditions, and confirming the surface state of the plating film layer to be generated.
  • a noble metal plating thin film layer (a second noble metal plating thin film layer) is newly formed on the outer peripheral side of the base metal plating thin film layer having an uneven surface with clear projections formed on the surface.
  • the metal tubule having a highly water-repellent surface of the present invention is used for collecting or testing a sample containing proteins or other components, such as a body fluid such as animal blood or serum.
  • a body fluid such as animal blood or serum
  • the outer peripheral surface of the base metal plating layer is desirably covered with a noble metal plating thin film layer.
  • the noble metal plating thin film layer on the outer peripheral surface of the base metal plating layer can be omitted, and a self-assembled monomolecular film having a water-repellent surface can be directly formed in a region having irregularities on the outer peripheral surface of the base metal plating layer.
  • the metal thin tube having the water-repellent outer peripheral surface in the region near the end instead of the metal thin tube having the water-repellent outer peripheral surface in the region near the end according to the present invention, it can also be used as a metal thin tube having a water-repellent outer peripheral surface in a region other than the end.
  • a self-assembled monomolecular film is formed in the region of the noble metal plating thin film layer, with an uneven surface having clear projections formed on the surface.
  • Examples of a compound (chain molecule) constituting a self-assembled monolayer having a water-repellent surface used for producing a metal thin tube having a highly water-repellent surface of the present invention include a thiol group at one end. And a compound having a hydrophobic group such as an alkyl group at the other end, a long-chain fatty acid such as stearic acid, or a salt thereof.
  • a compound having a hydrophobic group such as an alkyl group at the other end, a long-chain fatty acid such as stearic acid, or a salt thereof.
  • Many other compounds that can form a self-assembled monolayer having a water-repellent surface are known, and the self-assembled monolayer having an aqueous surface according to the present invention includes various types of these compounds. It can be formed using a compound.
  • the detailed description of the present invention in the present specification mainly describes a thin metal tube having a highly water-repellent region at least at one end and a peripheral region thereof, which is extremely useful as a micropipette or a microsyringe.
  • the present invention can also be used for producing a metal thin tube exhibiting high water repellency in a region other than the end portion and the periphery thereof.
  • Example 1 Manufacture of a thin tube composed of a composite plating film and a self-assembled monolayer A soft stainless steel wire (length: 600 mm, diameter: 0.5 mm) whose surface was cleaned was treated with gold.
  • a plating solution composition, potassium gold cyanide 4 g / L (as gold), potassium dihydrogen phosphate 60 g / L, potassium citrate 60 g / L, pH 6 to 8), solution temperature 60 ° C., current density 2 A /
  • a gold-plated thin film (average thickness: 0.1 ⁇ m) was formed on the peripheral surface.
  • the wire on which the gold plated thin film is formed is washed with water and dried, the wire is immersed in a nickel plating solution (composition: nickel sulfamate 450 g / L, nickel chloride 5 g / L, boric acid 35 g / L) to perform plating treatment.
  • a thick nickel plating film (average film thickness: 50 ⁇ m) was formed on the surface of the thin gold plating layer of the wire.
  • a wire was pulled out from the cylindrical composite film composed of the gold-plated thin film and the nickel-plated thick film to obtain a cylindrical plated-film composite (length: 500 mm) composed of the gold-plated thin film and the nickel-plated thick film.
  • this cylindrical plating film composite was cut into equal parts to produce 10 cylindrical plating film composites having a length of 50 mm.
  • Ten cylindrical plating film composites are vertically arranged using a jig, and each of the cylindrical plating films is plated with a nickel plating solution (pH: 1.5, composition: nickel chloride 200 g / L, boric acid 35 g / L). It was immersed to a height of 2 mm from the lower end of the membrane composite, and nickel plating was performed for 20 minutes under the processing conditions of a liquid temperature of 60 ° C. and a current density of 3 A / d square meter.
  • a nickel plating solution pH: 1.5, composition: nickel chloride 200 g / L, boric acid 35 g / L.
  • the lower end portion and the periphery thereof (the lower end portion, the outer peripheral surface and the inner peripheral surface following the lower end portion) of the nickel plating thick film of the cylindrical plating film composite are covered with a nickel plating thin film having an average film thickness of 5 ⁇ m. did. Observation of the surface of this nickel-plated thin film with a microscope showed that the cross-section was in a substantially triangular shape, the tip was sharp and sharp, and the bottom was in a rough surface state with countless projections that were continuous with each other. confirmed.
  • the gold plating solution used first is applied to the entire surface (all peripheral surfaces and both end surfaces) of the cylindrical plating film composite partially covered with the nickel plating thin film having a rough surface.
  • a gold plating solution having the same composition as above a gold plating thin film (average film thickness: 0.1 ⁇ m) was formed again under the same plating conditions. In this way, the coating of the gold plating thin film formed on the surface (peripheral surface) of the cylindrical plating film composite partially covered with the nickel plating thin film in a rough surface state is coated with the nickel plating thin film having a rough surface.
  • the surface of this gold-plated thin film also has a cross section of a substantially triangular shape, a sharply sharp tip, and a myriad of continuous shapes at the bottom. It was confirmed that the projections were in a rough surface state.
  • the region of the gold plating thin film having a region where the surface of the cylindrical plating film composite had a rough surface was immersed in a 3 mM aqueous solution of octadecanethiol for 48 hours, and then dried.
  • a self-assembled monomolecular film (SAM) of octadecanethiol was formed on the surface and the end face of the rough surface of the gold plating thin film of the cylindrical plating film composite.
  • FIG. 1 is a schematic diagram showing the configuration of a cylindrical or tubular body). In addition, an enlarged view of a portion where the self-assembled monolayer is formed is shown as a schematic diagram.
  • Example 2 Evaluation of the water repellency of a metal thin tube composed of the cylindrical plating film composite produced in Example 1 and a self-assembled monomolecular film
  • the cylindrical plating film composite produced in Example 1 A water supply pipe is connected to the upper end (the end on the side where the self-assembled monolayer is not formed) of the tubule composed of the self-assembled monolayer, and then, with the tubule arranged vertically, Water was supplied to the upper end of the thin tube, and the state of water discharge (dropping as water droplets) from the lower end of the thin tube was photographed using a high-speed camera. The obtained photograph is shown in FIG.
  • FIG. 2 shows that a thin tube composed of a cylindrical plating film composite having a water-repellent outer peripheral surface of the present invention and a self-assembled monomolecular film is vertically inserted.
  • 5 is a high-speed photograph of a state in which water is supplied to an upper end and water droplets immediately before falling from a lower end (an end on which a self-assembled monolayer is formed) are taken.
  • FIG. 3 shows a vertical view of a stainless steel tubule having substantially the same diameter as the tubule shown in FIG. 2, supplying water to the upper end, and photographing the state of water droplets immediately before falling from the lower end. It is a speed photography.
  • FIG. 1 shows that a thin tube composed of a cylindrical plating film composite having a water-repellent outer peripheral surface of the present invention and a self-assembled monomolecular film is vertically inserted.
  • 5 is a high-speed photograph of a state in which water is supplied to an upper end and water droplets immediately before falling from
  • FIG. 4 shows a vertical arrangement of the thin tube before forming the water-repellent self-assembled monolayer on the surface obtained in the process of manufacturing the thin tube having the water-repellent outer peripheral surface of the present invention shown in FIG. It is a high-speed photography photograph in which water is supplied to an upper end portion and a state of a water drop immediately before falling from a lower end portion is photographed. 3 and 4, it can be observed that a substantial portion of the water droplets discharged from the end of the thin tube has wrapped around the outer periphery of the thin tube.
  • Metal tube with water-repellent peripheral surface (cylindrical plating film composite) 2 First noble metal plating thin film layer 3 Base metal plating thick film layer 4 Base metal plating thin film layer with irregularities formed on the surface 5 Second noble metal plating thin film layer 6 Self-assembled monolayer

Abstract

[Problem] To provide a metal capillary which is provided in a region in the vicinity of an end portion thereof with a highly water-repellent surface, and which is particularly useful as a micro-pipette or a micro-syringe. [Solution] This metal capillary includes, in order from an inner circumferential side, a first tubular noble metal plated layer, a tubular base metal plated layer in which a rough surface having irregularities is formed on an outer circumferential surface in a region in the vicinity of an end portion thereof, and a second tubular noble metal plated layer having a rough surface in which irregularities are provided on an outer circumferential surface thereof, in the region in which the rough surface is formed on the tubular base metal plated layer, wherein a water-repellent self-assembled monolayer membrane is formed on the outer circumferential surface of the rough surface having irregularities, in the second tubular noble metal plated layer.

Description

端部に撥水性外周面を備えた金属製細管Metal tube with water-repellent peripheral surface at the end
　本発明は、少なくとも一方の端部に撥水性外周面を備えた金属製細管に関する。 The present invention relates to a thin metal tube having a water-repellent outer peripheral surface on at least one end.
　特許文献１には、ＬＳＩ等の集積回路の製造に必要な半導体パターンの検査に用いるコンタクトプローブを収容する極細の管体として有用な電鋳管を、周面に電解メッキにより金属導電層を設けたステンレス製の細線材の周りに、更に電鋳により電着物等を形成したのち、上記金属導電層を残して該ステンレス製細線材を引き抜いて除去する方法を利用して製造する方法が開示されている。この特許文献１には更に、上記の電鋳管が半導体産業以外のバイオテクノロジーや医療の分野にも使用できることの示唆もある。 Patent Literature 1 discloses an electroformed tube useful as an extremely fine tube for accommodating a contact probe used for inspection of a semiconductor pattern necessary for manufacturing an integrated circuit such as an LSI, and a metal conductive layer provided on an outer peripheral surface by electrolytic plating. A method is disclosed in which an electrodeposit or the like is further formed around the thin stainless steel wire by electroforming, and then the stainless thin wire is pulled out and removed while leaving the metal conductive layer. ing. This Patent Document 1 further suggests that the above-described electroformed tube can be used in the fields of biotechnology and medicine other than the semiconductor industry.
　特許文献２は、帯電による凝集が発生しにくい金属製細管の製造に関する開示があり、この金属製細管は、芯材の周囲に貴金属めっき処理することにより管状の貴金属めっき層を形成し、次いで芯材を除去する方法によって製造できることが記載されている。この特許文献２には、上記製法により得られる金属製細管の用途の例として、医療用カテーテルのＸ線不透過マーカー、半導体製造装置検査用コンタクトプローブのピンまたはバネを収容する管状部材が記載されている。 Patent Document 2 discloses a method of manufacturing a metal thin tube in which aggregation due to electrification is difficult to occur. This metal thin tube forms a tubular noble metal plating layer by performing a noble metal plating process around a core material, and then forms a core. It is described that it can be produced by a method of removing material. Patent Document 2 describes a tubular member for accommodating an X-ray opaque marker of a medical catheter, a pin or a spring of a contact probe for inspection of a semiconductor manufacturing apparatus, as an example of the use of a thin metal tube obtained by the above-described manufacturing method. ing.
　特許文献３には、超疎水性表面を備えるように金属品を被覆する方法であって、金属品の表面に自発的酸化還元反応などの方法を利用して他の金属で被覆した被覆層を形成し、次いでその金属被覆層の表面をチオール、ニトリルなどの疎水性材料に接触させる方法が記載されている。この特許文献３には、超疎水性表面が形成される金属品の例として、釘、バケツ、フォーク、ロッド、金属梁、金属ケーブル、レール、熱交換器の伝熱シート、セパレータ、フィルター、そして生物医学的用途として、ステント、カテーテル、創傷被覆材、中空のチューブまたは管、サンプリングシステムなどの例が記載されている。 Patent Literature 3 discloses a method of coating a metal article so as to have a superhydrophobic surface, wherein a coating layer coated with another metal on the surface of the metal article using a method such as a spontaneous oxidation-reduction reaction. It describes a method of forming and then contacting the surface of the metallization layer with a hydrophobic material such as thiol, nitrile or the like. Patent Document 3 discloses, as examples of metal articles on which a superhydrophobic surface is formed, nails, buckets, forks, rods, metal beams, metal cables, rails, heat transfer sheets for heat exchangers, separators, filters, and the like. Examples of biomedical applications include stents, catheters, wound dressings, hollow tubes or tubes, sampling systems, and the like.
特許第３８８９６８９号公報（発行日：平成１９年３月７日）Patent No. 3888989 (Date of issue: March 7, 2007) 特開２０１７－１２５２２４号公報JP-A-2017-125224 特許第５５８１０５１号公報（発行日：平成２６年８月２７日）Japanese Patent No. 5581051 (Date of issue: August 27, 2014)
　従来より、ミクロピペットやミクロシリンジ（ミクロ注射器）などを用いて、極微量の体液（血液、血清など）などの検査試料を採取したり、検査試料を分析機器に導入したり、あるいは極微量の薬液などを注入したりする技術が開発されているが、近年では医療技術や検査技術の発展に伴って、使用における迅速性や操作性が更に優れ、かつ定量性が向上したミクロピペットやミクロシリンジの開発が要求されている。 Conventionally, using a micropipette or microsyringe (micro syringe) to collect test samples such as trace amounts of body fluids (blood, serum, etc.), introduce test samples into analytical instruments, or Techniques for injecting chemicals and the like have been developed, but in recent years, with the development of medical technology and inspection technology, micropipette and microsyringe with even better use and operability and improved quantitativeness. Development is required.
　具体的には、ミクロピペットやミクロシリンジなどの医療検査や化学的検査に用いられる液体採取具や液体排出具の使用の際に、血液や試料液の定量的かつ迅速な採取操作や排出操作が実現することが望まれるが、それらの定量的かつ迅速なが採取操作や排出操作の実現を妨げる主要な原因として、ミクロピペットやミクロシリンジの先端部が示す高い親水性が挙げられる。 Specifically, when using a liquid sampling device or a liquid discharging device used for medical or chemical tests such as micropipette or microsyringe, quantitative and quick collection and drainage operations of blood and sample liquid are required. Although it is desirable to realize such a method, a major cause that hinders the realization of the sampling operation and the discharging operation in a quantitative and rapid manner is the high hydrophilicity of the tip of a micropipette or a microsyringe.
　すなわち、ミクロピペットやミクロシリンジは、高い定量性にて試料液の採取が可能なように、ステンレススチールなどの金属あるいはガラス材料を用いて製造されるが、通常の金属やガラス材料の表面は高い親水性を示すため、試料液に触れるミクロピペットやミクロシリンジの外周先端部の外周面に、採取あるいは排出した試料液が回り込み、このため、試料液の採取量や排出量の定量性が低下し易いという問題がある。 That is, a micropipette or a microsyringe is manufactured using a metal or glass material such as stainless steel so that a sample solution can be collected with high quantitativeness, but the surface of a normal metal or glass material is high. Because of its hydrophilicity, the collected or discharged sample liquid wraps around the outer peripheral surface of the outer end of the micropipette or microsyringe that comes into contact with the sample liquid, which reduces the quantitativeness of the collected and discharged sample liquid. There is a problem that it is easy.
　従って、本発明の課題は、ミクロピペットやミクロシリンジ等として好適に使用することのできる金属製細管であって、その外周面の先端部周辺領域が高い撥水性を示す金属製細管を提供することにある。 Therefore, an object of the present invention is to provide a metal thin tube that can be suitably used as a micropipette, a microsyringe, or the like, and that has a high water repellency in a peripheral region at a distal end portion of an outer peripheral surface thereof. It is in.
　本発明の発明者は、特許文献１や特許文献２に記載されているような電鋳管の製造技術を発展させた技術を利用して新たな構成の電鋳管を製造し、この電鋳管の表面の少なくとも一部（特に、外周面の先端部周辺領域）に高撥水化処理を施すことにより、ミクロピペットやミクロシリンジ等として好適に使用することのできる外周面の先端部周辺領域が優れた撥水性を示す金属製細管を製造することができることを見出し、本発明に到達した。 The inventor of the present invention manufactures an electroformed tube having a new configuration by utilizing the technology developed from the electroformed tube manufacturing technology described in Patent Document 1 or Patent Document 2, and manufactures the electroformed tube. By subjecting at least a part of the surface of the tube (particularly, a region around the distal end portion of the outer peripheral surface) to high water repellency treatment, a region around the distal end portion of the outer peripheral surface that can be suitably used as a micropipette, a micro syringe, or the like. Found that a thin metal tube exhibiting excellent water repellency can be produced, and arrived at the present invention.
　本発明の基礎となった発明者が新たに見出した事実とは、第一に、通常は、金属成形体や樹脂成形体に平滑な装飾性あるいは機能性表面を付与するために利用されるめっき処理を、金属材料あるいは合成樹脂材料から形成された芯材の外周面に対して、意図的に、平滑で無い表面が得られる条件を選択して施すことにより、表面に無数の突起が形成されて凹凸状となった表面（粗面）を持つ円筒状のめっき層（従って、表面積が増大した表面を持つめっき層となる）が再現性良く形成されるとの事実である。 The fact that the inventor based on the present invention has newly found out is, firstly, that plating usually used for imparting a smooth decorative property or a functional surface to a metal molding or a resin molding. By performing the treatment on the outer peripheral surface of the core material formed of a metal material or a synthetic resin material, intentionally, by selecting conditions that can obtain a non-smooth surface, countless projections are formed on the surface. This is a fact that a cylindrical plating layer having a roughened surface (rough surface) is formed with good reproducibility.
　そして、第二に、この円筒状のめっき面の表面の粗面に、自己組織化単分子膜（ＳＡＭ）の形成処理によって代表される表面の撥水性を向上させる表面特性改質処理を施すことによって、高い撥水性を示す外周面を持つ円筒体が得られるとの事実である。 Second, the rough surface of the cylindrical plating surface is subjected to a surface property modification treatment for improving the water repellency of the surface typified by a formation treatment of a self-assembled monolayer (SAM). It is a fact that a cylindrical body having an outer peripheral surface exhibiting high water repellency can be obtained.
　本発明の発明者はさらに研究を続け、極細の芯材の表面（外周面）にめっき処理を利用して金などの貴金属の薄膜層（表面が平滑であることが好ましい）を形成した後、その貴金属めっき薄膜層の表面にニッケルなどの卑金属のめっき厚膜層を生成させ、次いで、このように形成された貴金属めっき薄膜層と卑金属のめっき厚膜層との複合体を芯材から分離して、円筒状めっき複合体を得たのち、この円筒状めっき複合体の外周面に、外周面に凹凸を備えた粗面が形成された卑金属めっき薄膜層を形成し、そしてさらに卑金属めっき薄膜層の粗面の外周面に貴金属めっき薄膜層を形成したのち、撥水性を必要とする側の端部の近傍の外周面領域（卑金属めっき薄膜層の凹凸を備えた粗面の外周側となる領域）に自己組織化単分子膜（ＳＡＭ）を形成することによって、優れた撥水性を示す端部を備えた金属製細管が得られることを見出した。 The inventor of the present invention continued his research, and after forming a thin film layer (preferably having a smooth surface) of a noble metal such as gold on the surface (peripheral surface) of an extremely fine core material by using a plating process, A thick plating layer of a base metal such as nickel is formed on the surface of the noble metal plating thin film layer, and then a composite of the thus formed noble metal plating thin film layer and the thick plating layer of the base metal is separated from the core material. After obtaining a cylindrical plating composite, a base metal plating thin film layer having a rough surface with irregularities on the outer peripheral surface is formed on the outer peripheral surface of the cylindrical plating composite, and further, a base metal plating thin film layer is formed. After forming the noble metal plating thin film layer on the outer peripheral surface of the rough surface, the outer peripheral region near the end on the side where water repellency is required (the region on the outer peripheral side of the rough surface having irregularities of the base metal plating thin film layer) ) Is a self-assembled monolayer (SAM) By forming, it is obtained that with an end portion exhibiting excellent water repellency metal tubule.
　本発明の発明者は、上記の新しい知見に基づき、更に研究を続けた結果、上記の方法により製造することができる、少なくとも一方の端部の近傍領域の外周面が優れた撥水性を示し、例えば、ミクロピペットやミクロシリンジとして有利に使用することができる金属製細管を製造することに成功した。 The inventors of the present invention, based on the above new findings, as a result of further research, can be produced by the above method, the outer peripheral surface of the region near at least one end shows excellent water repellency, For example, they have succeeded in manufacturing a metal thin tube that can be advantageously used as a micropipette or a microsyringe.
　従って、本発明は、以下に記載する撥水性外周面を備えた金属製細管にある。
　内周側から順に、第一の管状貴金属めっき層、少なくとも一方の端部の近傍領域の外周面に凹凸を持つ粗面が形成された管状卑金属めっき層、そして上記の管状卑金属めっき層の粗面が形成された領域の外周面に凹凸を備えた粗面を持つ第二の管状貴金属めっき層を含む金属製細管であって、第二の管状貴金属めっき層の凹凸を持つ粗面の外周面に撥水性の自己組織化単分子膜が形成されている、端部の近傍領域に撥水性外周面を備えた金属製細管。 Therefore, the present invention resides in a thin metal tube having a water-repellent outer peripheral surface described below.
In order from the inner peripheral side, a first tubular noble metal plating layer, a tubular base metal plating layer in which a rough surface having irregularities is formed on an outer peripheral surface in a region near at least one end, and a rough surface of the above tubular base metal plating layer Is a metal thin tube including a second tubular noble metal plating layer having a rough surface with irregularities on the outer peripheral surface of the region where is formed, the outer peripheral surface of the rough surface with irregularities of the second tubular noble metal plating layer A thin metal tube having a water-repellent outer peripheral surface in a region near an end, on which a water-repellent self-assembled monolayer is formed.
　上記の本発明に従う端部の近傍領域に撥水性外周面を備えた金属製細管の好ましい態様は次の通りである。
（１）上記の管状卑金属めっき層が、内周側の管状卑金属めっき厚膜層と、その外周側に形成された少なくとも一方の端部の近傍領域の外周面に凹凸を持つ粗面を備える管状卑金属めっき薄膜層を含む。
（２）撥水性の自己組織化単分子膜が、管状卑金属めっき層の凹凸を持つ粗面が形成された領域の近傍に接する端面も被覆するように形成されている。
（３）撥水性の自己組織化単分子膜が、管状卑金属めっき層の凹凸を持つ粗面が形成された領域の近傍の端面、そしてその端面に続く第一の管状貴金属めっき層の内周面の少なくとも一部を被覆するように形成されている。
（４）第一の管状貴金属めっき層が金めっき層である。
（５）管状卑金属めっき層がニッケルめっき層である。
（６）端部の近傍領域に撥水性外周面を備えた金属製細管ミクロピペットもしくはミクロシリンジである。 Preferred embodiments of the above-described metal thin tube having a water-repellent outer peripheral surface in the region near the end according to the present invention are as follows.
(1) The above-mentioned tubular base metal plating layer has a tubular base metal plating thick film layer on the inner peripheral side and a rough surface having irregularities on the outer peripheral surface in a region near at least one end formed on the outer peripheral side. Including a base metal plating thin film layer.
(2) The water-repellent self-assembled monomolecular film is formed so as to cover the end surface of the tubular base metal plating layer which is in contact with the vicinity of the region where the roughened surface having irregularities is formed.
(3) The water-repellent self-assembled monomolecular film has an end surface near the region where the rough surface having irregularities of the tubular base metal plating layer is formed, and the inner peripheral surface of the first tubular noble metal plating layer following the end surface. Is formed so as to cover at least a part of.
(4) The first tubular noble metal plating layer is a gold plating layer.
(5) The tubular base metal plating layer is a nickel plating layer.
(6) A metal capillary micropipette or microsyringe provided with a water-repellent outer peripheral surface in a region near the end.
　前記の端部の近傍領域に撥水性外周面を備えた金属製細管は下記の方法を利用することにより、容易に製造することができる。
　芯材の外周面に第一の貴金属めっき薄膜層を形成する工程、この貴金属めっき薄膜層の外周面に卑金属めっき厚膜層を形成する工程、これらの工程により形成された貴金属めっき薄膜層と卑金属めっき厚膜層の複合層から前記芯材を除去して円筒状めっき複合体を得る工程、この円筒状めっき複合体の卑金属めっき厚膜層の外周面に、少なくとも一方の端部の近傍領域に凹凸を備える粗面を持つ卑金属めっき薄膜層を形成する工程、この卑金属めっき薄膜層の粗面を持つ領域の外周面を第二の貴金属めっき薄膜層で被覆することにより、当該領域に凹凸表面を備える粗面を持つ貴金属めっき薄膜層を形成する工程、そして、この貴金属めっき薄膜層の粗面を持つ領域の外周面に撥水性の自己組織化単分子膜を形成する工程を含む方法。 A thin metal tube having a water-repellent outer peripheral surface in the vicinity of the end can be easily manufactured by using the following method.
A step of forming a first noble metal plating thin film layer on the outer peripheral surface of the core material, a step of forming a base metal plating thick film layer on the outer peripheral surface of the noble metal plating thin film layer, a noble metal plating thin film layer formed by these steps and a base metal Removing the core material from the composite layer of the plating thick film layer to obtain a cylindrical plating composite, on the outer peripheral surface of the base metal plating thick film layer of the cylindrical plating composite, in a region near at least one end; Forming a base metal plating thin film layer having a rough surface with irregularities, by coating the outer peripheral surface of the region having the rough surface of the base metal plating thin film layer with a second noble metal plating thin film layer, thereby forming an uneven surface in the region; Forming a noble metal plating thin film layer having a rough surface provided thereon; and forming a water-repellent self-assembled monolayer on the outer peripheral surface of the roughened region of the noble metal plating thin film layer.
　なお、第一の管状貴金属めっき薄膜層と第二の管状貴金属めっき薄膜層の層厚（平均層厚）はいずれも０．０１～１μｍの範囲にあることが好ましく、そして貴金属めっき薄膜層の外周面に形成される卑金属めっき厚膜層の層厚は、５～５００μｍの範囲にあることが好ましい。また、卑金属めっき厚膜層の外周面に形成される、凹凸表面を持つ卑金属めっき薄膜層は、卑金属めっき厚膜層よりも層厚が小さいめっき層であって、その層厚は１～５０μｍの範囲にあることが好ましい。なお、凹凸表面を持つ卑金属めっき薄膜層の層厚とは、その底面から、卑金属メッキ薄膜層の凹凸面の平均高さまでの平均距離（平均高さ）を意味する。
　また、本明細書において、特に注記しない限り、「めっき」とは「電気めっき」を意味する。 The thickness (average layer thickness) of each of the first tubular noble metal plating thin film layer and the second tubular noble metal plating thin film layer is preferably in the range of 0.01 to 1 μm. The thickness of the base metal plating thick film layer formed on the surface is preferably in the range of 5 to 500 μm. Further, the base metal plating thin film layer having an uneven surface formed on the outer peripheral surface of the base metal plating thick film layer is a plating layer having a smaller thickness than the base metal plating thick film layer, and has a thickness of 1 to 50 μm. It is preferably within the range. The layer thickness of the base metal plating thin film layer having an uneven surface means an average distance (average height) from the bottom surface to the average height of the uneven surface of the base metal plating thin film layer.
In this specification, “plating” means “electroplating” unless otherwise specified.
　本発明の少なくとも一方の端部に撥水性外周面を備えた金属製細管は、撥水性の自己組織化単分子膜が形成された領域（すなわち、細管の端部や、その近傍領域、例えば、端部に接する外周面や内周面の領域）で高い撥水性を示す。従って、高い定量性にて試料の採取や注入を行うためのミクロピペットやミクロシリンジなどとして極めて有用である。 The metal thin tube provided with a water-repellent outer peripheral surface on at least one end of the present invention is a region where a water-repellent self-assembled monomolecular film is formed (that is, an end of the thin tube or a region in the vicinity thereof, for example, High water repellency at the outer peripheral surface and the inner peripheral surface in contact with the end portion). Therefore, it is extremely useful as a micropipette, a microsyringe, or the like for collecting or injecting a sample with high quantitativeness.
本発明の少なくとも一方の端部に撥水性外周面を備えた金属製細管の断面図であり、その金属製細管を構成する複数のめっき膜と自己組織化単分子膜との積層構造を示す図である。なお、拡大図（模式図）も添付した。　図１において、撥水性外周面を備えた金属製細管１は、最内周側から、第一の貴金属めっき薄膜層２、卑金属めっき厚膜層３、表面に凹凸が形成された卑金属めっき薄膜層４、第二の貴金属めっき薄膜層５、そして自己組織化単分子膜６から構成されている。FIG. 2 is a cross-sectional view of a metal thin tube having a water-repellent outer peripheral surface on at least one end of the present invention, showing a stacked structure of a plurality of plating films and a self-assembled monomolecular film constituting the metal thin tube. It is. An enlarged view (schematic view) is also attached. In FIG. 1, a metal thin tube 1 having a water-repellent outer peripheral surface has a first noble metal plating thin film layer 2, a base metal plating thick film layer 3, and a base metal plating thin film layer having irregularities formed on the surface from the innermost peripheral side. 4, a second noble metal plated thin film layer 5 and a self-assembled monolayer 6. 本発明の撥水性外周面を備えた金属製細管を垂直に配置し、上端部に水を供給して、下端部から水滴が落下する直前の状態を撮影した高速度撮影写真を示す。Fig. 4 shows a high-speed photograph of a state in which a thin metal tube having a water-repellent outer peripheral surface of the present invention is vertically arranged, water is supplied to an upper end portion, and a state immediately before a water drop falls from a lower end portion. 図２に示した金属製細管と略同径のステンレススチール製細管を垂直に配置し、上端部から水を供給して、下端部から水滴が落下する直前の状態を撮影した高速度撮影写真を示す。A high-speed photograph of a state in which a stainless steel thin tube having substantially the same diameter as the metal thin tube shown in FIG. 2 is vertically arranged, water is supplied from an upper end portion, and a state immediately before a water drop falls from a lower end portion. Show. 図２に示した本発明の撥水性外周面を備えた金属製細管の製造過程で得られた表面に撥水性の自己組織化単分子膜を形成する前の金属製細管を垂直に配置し、上端部に水を供給して、下端部から水滴が落下する直前の状態を撮影した高速度撮影写真を示す。The metal thin tube before forming the water-repellent self-assembled monomolecular film on the surface obtained in the process of manufacturing the metal thin tube having the water-repellent outer peripheral surface of the present invention shown in FIG. The high-speed photography which image | photographed the state just before water was supplied from the lower end part and water was supplied to the upper end part is shown.
　次に、本発明の撥水性外周面を備えた金属製細管を製造するための材料および方法などを詳しく説明する。 Next, a material and a method for manufacturing a metal thin tube having a water-repellent outer peripheral surface of the present invention will be described in detail.
　本発明の撥水性外周面を備えた金属製細管の製造に際しては、まず芯材として用いる線状材料の周囲に、電気めっき法を利用して、貴金属めっき薄膜層（第一の貴金属めっき薄膜層）と卑金属めっき厚膜層（表面に凹凸を備える粗面が形成されていてもよい）を順次形成することによりめっき複合体を得たのち、そのめっき層複合体から、芯材を引き抜く、あるいは溶解除去するなどの操作によって円筒状めっき複合体を分離する。そして、その円筒状めっき複合体のすくなくとも一方の端部の近傍の領域に、表面に凹凸を備える粗面を持つ卑金属めっき薄膜層を形成し、その後、その卑金属めっき薄膜層の外周面に改めて貴金属めっき薄膜層（第二の貴金属めっき薄膜層）を形成する。このようにして形成された第二の貴金属めっき薄膜層は、必然的に、卑金属めっき薄膜層の凹凸を備える粗面の外周側となる領域の表面で、凹凸を備える粗面となる。そして、最後に第二の貴金属めっき薄膜層の表面に撥水性の自己組織化単分子膜を積層する。 When manufacturing the metal thin tube having the water-repellent outer peripheral surface of the present invention, first, a noble metal plated thin film layer (first noble metal plated thin film layer) is formed around a linear material used as a core material by using an electroplating method. ) And a base metal plating thick film layer (a rough surface having irregularities may be formed on the surface) in order to obtain a plating composite, and then pulling out a core material from the plating layer composite, or The cylindrical plating composite is separated by an operation such as dissolution removal. Then, a base metal plating thin film layer having a rough surface having irregularities on its surface is formed in at least a region near one end of the cylindrical plating composite, and then a precious metal is formed on the outer peripheral surface of the base metal plating thin film layer again. A plating thin film layer (second noble metal plating thin film layer) is formed. The second noble metal plating thin film layer formed in this manner inevitably becomes a rough surface having irregularities on the outer peripheral side of the rough surface having irregularities of the base metal plating thin film layer. Finally, a water-repellent self-assembled monolayer is laminated on the surface of the second noble metal plating thin film layer.
　上記の製造方法において、用いる芯材としては、ステンレススチールなどの金属からなる芯材やポリアミド樹脂などの合成樹脂を線状に成形した芯材を挙げることができる。なお、円筒状めっき複合体の製造に用いる芯材については、先に記載した特許文献１と特許文献２に記載があるので、それらの記載内容を本明細書の記載とする。 に お い て In the above manufacturing method, examples of the core material used include a core material made of a metal such as stainless steel and a core material obtained by forming a synthetic resin such as a polyamide resin into a linear shape. In addition, since the core material used for manufacturing the cylindrical plating composite is described in Patent Document 1 and Patent Document 2 described above, the contents of those descriptions are described in this specification.
　貴金属めっき薄膜層（第一の貴金属めっき薄膜層および第二の貴金属めっき薄膜層）の形成に用いる貴金属材料としては特に限定はないが、その例としては、金（Ａｕ）、白金（Ｐｔ）、銀（Ａｇ）、そしてパラジウム（Ｐｄ）からなる群より選ばれる一種以上の貴金属、特に金、を挙げることができる。またはＡｕ－Ｆｅ、Ａｕ－Ｗ、Ａｕ－Ｃｏ、Ａｕ－Ｎｉ、Ａｕ－Ａｇなどの、主要成分である金などの貴金属と他の貴金属あるいは卑金属を少量成分とする合金を用いることもできる。 The noble metal material used for forming the noble metal plating thin film layer (the first noble metal plating thin film layer and the second noble metal plating thin film layer) is not particularly limited, and examples thereof include gold (Au), platinum (Pt), One or more noble metals selected from the group consisting of silver (Ag) and palladium (Pd), in particular, gold can be mentioned. Alternatively, an alloy containing a noble metal such as gold as a main component and another noble metal or a base metal as a small component such as Au-Fe, Au-W, Au-Co, Au-Ni, or Au-Ag can also be used.
　芯材の外周面に形成する貴金属めっき薄膜層（第一の貴金属めっき薄膜層）の厚み（平均層厚）は０．０１～１μｍの範囲にあることが好ましい。 厚 み The thickness (average layer thickness) of the noble metal plating thin film layer (first noble metal plating thin film layer) formed on the outer peripheral surface of the core material is preferably in the range of 0.01 to 1 μm.
　芯材の外周面の貴金属めっき薄膜層（第一の貴金属めっき薄膜層）の周囲には、卑金属めっき厚膜層（表面が平滑なめっき厚膜層であって良いが、表面に凹凸面を備えた粗面を持つ卑金属めっき厚膜層であってもよい）が形成される。この卑金属めっき厚膜層は、公知の卑金属めっき層の形成方法を利用して得ることができる。卑金属めっき層の形成に利用できる卑金属材料の例としては、ニッケル（Ｎｉ）、ニッケルと鉄の合金（Ｎｉ－Ｆｅ）、ニッケルとタングステンの合金（Ｎｉ－Ｗ）、ニッケルとコバルトの合金（Ｎｉ－Ｃｏ）、そしてニッケルとマンガンとの合金（Ｎｉ－Ｍｎ）を挙げることができる。 Around the noble metal plating thin film layer (first noble metal plating thin film layer) on the outer peripheral surface of the core material, a base metal plating thick film layer (a plating thick film layer having a smooth surface may be provided. (A thick base metal plating layer having a rough surface). This base metal plating thick film layer can be obtained by using a known method for forming a base metal plating layer. Examples of the base metal material that can be used for forming the base metal plating layer include nickel (Ni), an alloy of nickel and iron (Ni-Fe), an alloy of nickel and tungsten (Ni-W), and an alloy of nickel and cobalt (Ni-W). Co) and an alloy of nickel and manganese (Ni—Mn).
　卑金属めっき厚膜層の層厚は、２０～５００μｍの範囲にあることが好ましい。 The thickness of the base metal plating thick film layer is preferably in the range of 20 to 500 μm.
　次に、前述のように、芯材の外周面に形成された貴金属めっき薄膜層（第一の貴金属めっき薄膜層）とその貴金属めっき薄膜層との外周面に形成された卑金属めっき厚膜層との円筒状（あるいは管状）積層体から、芯材を除去することにより、貴金属めっき薄膜層とその貴金属めっき薄膜層との外周面に形成された卑金属めっき厚膜層とからなる複合めっき円筒体（管状体）が得られる。 Next, as described above, the noble metal plating thin film layer (first noble metal plating thin film layer) formed on the outer peripheral surface of the core material and the base metal plating thick film layer formed on the outer peripheral surface of the noble metal plating thin film layer By removing the core material from the cylindrical (or tubular) laminated body of the above, a composite plating cylinder comprising a noble metal plating thin film layer and a base metal plating thick film layer formed on the outer peripheral surface of the noble metal plating thin film layer ( Tubular body) is obtained.
　複合めっき円筒体（環状体）の卑金属めっき厚膜層の表面に明確な突起を備えた凹凸面が形成されていない場合には、円筒体の端部およびその周囲の領域に、明確な突起を備えた凹凸面(粗面）を持つ卑金属めっき薄膜層（層厚は、一般に０．５～２０μｍ）を形成する。この表面に明確な突起を備えた凹凸面が形成された卑金属めっき薄膜層は、従来より知られている卑金属めっき層の形成に利用される条件とは異なる条件を利用することにより得ることができる。なお、そのような条件は、めっき液の組成や各種のめっき操作条件により変動するので一概には決められない。当業者であれば、本明細書に記載の実施例を参考にし、また処理条件を変え、生成するめっき膜層の表面状態を確認することにより、容易に決めることができる。 When the surface of the base metal plating thick film layer of the composite plating cylinder (annular body) does not have an uneven surface having a distinct projection, a distinct projection is formed on the end of the cylinder and the surrounding area. A base metal plated thin film layer (layer thickness is generally 0.5 to 20 μm) having the provided uneven surface (rough surface) is formed. The base metal plating thin film layer on which the uneven surface with clear projections is formed on the surface can be obtained by using conditions different from those conventionally used for forming a base metal plating layer. . Note that such conditions vary depending on the composition of the plating solution and various plating operation conditions, and thus cannot be unconditionally determined. Those skilled in the art can easily determine the conditions by referring to the examples described in the present specification, changing the processing conditions, and confirming the surface state of the plating film layer to be generated.
　表面に明確な突起を備えた凹凸面が形成された卑金属めっき薄膜層、の外周側には、改めて貴金属めっき薄膜層（第二の貴金属めっき薄膜層）が形成される。たとえば、本発明の高撥水性表面を備えた金属製細管を動物の血液や血清などの体液のような、蛋白質あるいは他の成分が含有されている試料の採取や検査操作に利用する場合には、それらの試料と金属製細管の表面との間での化学反応を回避するためには、金属製細管の表面に卑金属めっき層が露出することは避けるべきであるため、卑金属めっき層の外周面は貴金属めっき薄膜層で被覆することが望ましい。
　ただし、卑金属めっき層の外周面への貴金属めっき薄膜層を省略して、卑金属めっき層の外周面の凹凸を備えた領域に撥水性表面を持つ自己組織化単分子膜を直接形成することもできる。
　また、本発明の端部の近傍領域に撥水性外周面を備えた金属製細管の代わりに、端部以外の領域に撥水性外周面を備えた金属製細管としても利用することができる。 A noble metal plating thin film layer (a second noble metal plating thin film layer) is newly formed on the outer peripheral side of the base metal plating thin film layer having an uneven surface with clear projections formed on the surface. For example, when the metal tubule having a highly water-repellent surface of the present invention is used for collecting or testing a sample containing proteins or other components, such as a body fluid such as animal blood or serum, In order to avoid a chemical reaction between the sample and the surface of the metal thin tube, it is necessary to avoid exposing the base metal plating layer on the surface of the metal thin tube, and therefore, the outer peripheral surface of the base metal plating layer. Is desirably covered with a noble metal plating thin film layer.
However, the noble metal plating thin film layer on the outer peripheral surface of the base metal plating layer can be omitted, and a self-assembled monomolecular film having a water-repellent surface can be directly formed in a region having irregularities on the outer peripheral surface of the base metal plating layer. .
Further, instead of the metal thin tube having the water-repellent outer peripheral surface in the region near the end according to the present invention, it can also be used as a metal thin tube having a water-repellent outer peripheral surface in a region other than the end.
　表面に明確な突起を備えた凹凸面が形成され貴金属めっき薄膜層の領域には、自己組織化単分子膜が形成される。 (4) A self-assembled monomolecular film is formed in the region of the noble metal plating thin film layer, with an uneven surface having clear projections formed on the surface.
　本発明の高撥水性表面を備えた金属製細管の製造に利用される撥水性表面を持つ自己組織化単分子膜を構成する化合物（鎖状分子）の例としては、一方の末端にチオール基を持ち、他方の末端にアルキル基などの疎水性基を持つ化合物、ステアリン酸などの長鎖脂肪酸もしくはその塩を挙げることができる。なお、撥水性表面を持つ自己組織化単分子膜を形成することができる化合物は、他にの多数知られており、本発明の水性表面を持つ自己組織化単分子膜は、それらの各種の化合物を用いて形成することができる。 Examples of a compound (chain molecule) constituting a self-assembled monolayer having a water-repellent surface used for producing a metal thin tube having a highly water-repellent surface of the present invention include a thiol group at one end. And a compound having a hydrophobic group such as an alkyl group at the other end, a long-chain fatty acid such as stearic acid, or a salt thereof. Many other compounds that can form a self-assembled monolayer having a water-repellent surface are known, and the self-assembled monolayer having an aqueous surface according to the present invention includes various types of these compounds. It can be formed using a compound.
　なお、本明細書での本発明の詳しい説明は、ミクロピペットやミクロシリンジなどとして極めて有用な、少なくとも一方の端部とその周辺の領域に高い撥水性領域を備えた金属製細管を中心に記載したが、本発明は、端部とその周辺以外の領域で高い撥水性を示す金属製細管の製造に利用することもできる。 Note that the detailed description of the present invention in the present specification mainly describes a thin metal tube having a highly water-repellent region at least at one end and a peripheral region thereof, which is extremely useful as a micropipette or a microsyringe. However, the present invention can also be used for producing a metal thin tube exhibiting high water repellency in a region other than the end portion and the periphery thereof.
［実施例１］複合めっき膜と自己組織化単分子膜とから構成された細管の製造
　表面を清浄化処理した軟質のステンレススチール製ワイヤ（長さ：６００ｍｍ、径：０．５ｍｍ）を、金めっき液（組成、シアン化金カリウム４ｇ／Ｌ（金として）、リン酸二水素カリウム６０ｇ／Ｌ、クエン酸カリウム６０ｇ／Ｌ、ｐＨ６～８）に浸漬し、液温６０℃、電流密度２Ａ／ｄ平方メートルの処理条件にて、その周面に金めっき薄膜（平均膜厚：０．１μｍ）を形成した。この金めっき薄膜が形成されたワイヤを水洗乾燥させた後、今度はニッケルめっき液（組成：スルファミン酸ニッケル４５０ｇ／Ｌ、塩化ニッケル５ｇ／Ｌ、硼酸３５ｇ／Ｌ）に浸漬してめっき処理を行い、ワイヤの金めっき薄層の表面にニッケルめっき厚膜（平均膜厚：５０μｍ）を形成した。次いで、金めっき薄膜とニッケルめっき厚膜とからなる円筒状の複合膜からワイヤを引き抜き、金めっき薄膜とニッケルめっき厚膜とからなる円筒状めっき膜複合体（長さ：５００ｍｍ）を得た。 [Example 1] Manufacture of a thin tube composed of a composite plating film and a self-assembled monolayer A soft stainless steel wire (length: 600 mm, diameter: 0.5 mm) whose surface was cleaned was treated with gold. Immersion in a plating solution (composition, potassium gold cyanide 4 g / L (as gold), potassium dihydrogen phosphate 60 g / L, potassium citrate 60 g / L, pH 6 to 8), solution temperature 60 ° C., current density 2 A / Under a processing condition of d square meters, a gold-plated thin film (average thickness: 0.1 μm) was formed on the peripheral surface. After the wire on which the gold plated thin film is formed is washed with water and dried, the wire is immersed in a nickel plating solution (composition: nickel sulfamate 450 g / L, nickel chloride 5 g / L, boric acid 35 g / L) to perform plating treatment. A thick nickel plating film (average film thickness: 50 μm) was formed on the surface of the thin gold plating layer of the wire. Next, a wire was pulled out from the cylindrical composite film composed of the gold-plated thin film and the nickel-plated thick film to obtain a cylindrical plated-film composite (length: 500 mm) composed of the gold-plated thin film and the nickel-plated thick film.
　次に、この円筒状めっき膜複合体を等分に切断して、長さ５０ｍｍの円筒状めっき膜複合体を１０本作製した。 Next, this cylindrical plating film composite was cut into equal parts to produce 10 cylindrical plating film composites having a length of 50 mm.
　上記の円筒状めっき膜複合体１０本を治具を用いて垂直に配列させ、ニッケルめっき液（ｐＨ：１．５、組成：塩化ニッケル２００ｇ／Ｌ、硼酸３５ｇ／Ｌ）に、各円筒状めっき膜複合体の下端部から２ｍｍの高さまで浸漬し、液温６０℃、電流密度３Ａ／ｄ平方メートルの処理条件にて、２０分間かけてニッケルめっき処理を行った。このめっき処理により、円筒状めっき膜複合体のニッケルめっき厚膜の表面の下端部とその周辺（下端部とそれに続く外周面と内周面）とを、平均膜厚５μｍのニッケルめっき薄膜で被覆した。
　このニッケルめっき薄膜の表面を顕微鏡で観察したところ、断面が略三角形の形状にあり、先端が鋭く尖り、底部で互いに連続している無数の突起が形成された粗面状態となっていることが確認された。 Ten cylindrical plating film composites are vertically arranged using a jig, and each of the cylindrical plating films is plated with a nickel plating solution (pH: 1.5, composition: nickel chloride 200 g / L, boric acid 35 g / L). It was immersed to a height of 2 mm from the lower end of the membrane composite, and nickel plating was performed for 20 minutes under the processing conditions of a liquid temperature of 60 ° C. and a current density of 3 A / d square meter. By this plating treatment, the lower end portion and the periphery thereof (the lower end portion, the outer peripheral surface and the inner peripheral surface following the lower end portion) of the nickel plating thick film of the cylindrical plating film composite are covered with a nickel plating thin film having an average film thickness of 5 μm. did.
Observation of the surface of this nickel-plated thin film with a microscope showed that the cross-section was in a substantially triangular shape, the tip was sharp and sharp, and the bottom was in a rough surface state with countless projections that were continuous with each other. confirmed.
　続いて、このようにして表面が粗面状態にあるニッケルめっき薄膜で部分的に被覆された円筒状めっき膜複合体の全表面（全周面と両端面）に、最初に使用した金めっき液と同組成の金めっき液を用いて、同様のめっき処理条件にて改めて金めっき薄膜（平均膜厚：０．１μｍ）を形成した。このようにして粗面状態にあるニッケルめっき薄膜で部分的に被覆された円筒状めっき膜複合体の表面（周面）に形成された金めっき薄膜の、表面が粗面のニッケルめっき薄膜の被覆層となっている領域の表面について、その表面を顕微鏡で観察したところ、この金めっき薄膜の表面もまた、断面が略三角形の形状にあり、先端が鋭く尖り、底部で互いに連続している無数の突起が形成された粗面状態にあることが確認された。 Subsequently, the gold plating solution used first is applied to the entire surface (all peripheral surfaces and both end surfaces) of the cylindrical plating film composite partially covered with the nickel plating thin film having a rough surface. Using a gold plating solution having the same composition as above, a gold plating thin film (average film thickness: 0.1 μm) was formed again under the same plating conditions. In this way, the coating of the gold plating thin film formed on the surface (peripheral surface) of the cylindrical plating film composite partially covered with the nickel plating thin film in a rough surface state is coated with the nickel plating thin film having a rough surface. When observing the surface of the layered region with a microscope, the surface of this gold-plated thin film also has a cross section of a substantially triangular shape, a sharply sharp tip, and a myriad of continuous shapes at the bottom. It was confirmed that the projections were in a rough surface state.
　最後に、円筒状めっき膜複合体の表面が粗面状態にある領域を持つ金めっき薄膜の当該領域をオクタデカンチオール３ｍＭ水溶液に４８時間浸漬させ、次いで乾燥させた。この処理により、円筒状めっき膜複合体の金めっき薄膜の粗面状態にある表面領域の表面と端面とにオクタデカンチオールの自己組織化単分子膜（ＳＡＭ）が形成された。 Finally, the region of the gold plating thin film having a region where the surface of the cylindrical plating film composite had a rough surface was immersed in a 3 mM aqueous solution of octadecanethiol for 48 hours, and then dried. By this treatment, a self-assembled monomolecular film (SAM) of octadecanethiol was formed on the surface and the end face of the rough surface of the gold plating thin film of the cylindrical plating film composite.
　このようにして作製した円筒状めっき膜複合体と、その一方の端部周辺の領域に形成された自己組織化単分子膜とから構成された細管（内径：約０．５ｍｍ、外径：約０．５ｍｍ、最内周側から、金めっき薄膜、ニッケルめっき厚膜、ニッケルめっき薄膜（一部領域）、金めっき薄膜、そして自己組織化単分子膜（一部領域）が積層されて形成された円筒体もしくは管状体）の構成を図１に模式図として示す。また、併せて、自己組織化単分子膜が形成された部分の拡大図を模式図としてして示した。 A thin tube (inner diameter: about 0.5 mm, outer diameter: about 0.5 mm) composed of the cylindrical plating film composite thus produced and the self-assembled monomolecular film formed in a region around one end thereof. 0.5 mm, gold-plated thin film, nickel-plated thick film, nickel-plated thin film (partial region), gold-plated thin film, and self-assembled monolayer (partial region) are laminated and formed from the innermost side FIG. 1 is a schematic diagram showing the configuration of a cylindrical or tubular body). In addition, an enlarged view of a portion where the self-assembled monolayer is formed is shown as a schematic diagram.
［実施例２］実施例１で製造した円筒状めっき膜複合体と自己組織化単分子膜とから構成された金属製細管の撥水性の評価
　実施例１で製造した円筒状めっき膜複合体と自己組織化単分子膜とから構成された細管の上端部（自己組織化単分子膜が形成されていない側の端部）に給水パイプを接続し、次いでその細管を垂直に配置した状態で、細管上端部に水を供給し、細管下端部からの水の排出（水滴としての落下）の状態を、高速度カメラを用いて撮影した。得られた写真を、図２に示す。細管下端部から排出する水滴の大部分が細管の外周部に回り込むこと無く、落下していることが観察される。
　次に、上記の本発明の撥水性外周面を備えた細管と略同径のステンレススチール製細管、そして上記の撥水性外周面を備えた金属製細管の製造過程で得られた表面に自己組織化単分子膜を形成していない円筒状めっき膜複合体についても、同様な方法で、その撥水性を観察した。得られた写真をそれぞれ、図３と図４に示す。 [Example 2] Evaluation of the water repellency of a metal thin tube composed of the cylindrical plating film composite produced in Example 1 and a self-assembled monomolecular film The cylindrical plating film composite produced in Example 1 A water supply pipe is connected to the upper end (the end on the side where the self-assembled monolayer is not formed) of the tubule composed of the self-assembled monolayer, and then, with the tubule arranged vertically, Water was supplied to the upper end of the thin tube, and the state of water discharge (dropping as water droplets) from the lower end of the thin tube was photographed using a high-speed camera. The obtained photograph is shown in FIG. It is observed that most of the water droplets discharged from the lower end of the thin tube fall without going around the outer periphery of the thin tube.
Next, the surface obtained in the process of manufacturing the stainless steel thin tube having substantially the same diameter as the thin tube having the water-repellent outer peripheral surface of the present invention and the metal thin tube having the above water-repellent outer peripheral surface has a self-organizing structure. The water repellency of the cylindrical plating film composite on which no functionalized monomolecular film was formed was observed in the same manner. The obtained photographs are shown in FIGS. 3 and 4, respectively.
　なお、ここで図２乃至図４についてまとめて説明すると、図２が、本発明の撥水性外周面を備えた円筒状めっき膜複合体と自己組織化単分子膜とから構成された細管を垂直に配置し、上端部に水を供給して、下端部（自己組織化単分子膜が形成された端部）から落下する直前の水滴の状態を撮影した高速度撮影写真である。
　そして、図３が、図２に示した細管と略同径のステンレススチール製細管を垂直に配置し、上端部に水を供給して、下端部から落下する直前の水滴の状態を撮影した高速度撮影写真である。
　なお、図４は、図２に示した本発明の撥水性外周面を備えた細管の製造過程で得られた表面に撥水性の自己組織化単分子膜を形成する前の細管を垂直に配置し、上端部に水を供給して、下端部から落下する直前の水滴の状態を撮影した高速度撮影写真である。
　図３と図４では、細管の端部から排出する水滴の相当部分が細管の外周部に回り込んでいることが観察される。 FIG. 2 to FIG. 4 will be described collectively. FIG. 2 shows that a thin tube composed of a cylindrical plating film composite having a water-repellent outer peripheral surface of the present invention and a self-assembled monomolecular film is vertically inserted. 5 is a high-speed photograph of a state in which water is supplied to an upper end and water droplets immediately before falling from a lower end (an end on which a self-assembled monolayer is formed) are taken.
FIG. 3 shows a vertical view of a stainless steel tubule having substantially the same diameter as the tubule shown in FIG. 2, supplying water to the upper end, and photographing the state of water droplets immediately before falling from the lower end. It is a speed photography.
FIG. 4 shows a vertical arrangement of the thin tube before forming the water-repellent self-assembled monolayer on the surface obtained in the process of manufacturing the thin tube having the water-repellent outer peripheral surface of the present invention shown in FIG. It is a high-speed photography photograph in which water is supplied to an upper end portion and a state of a water drop immediately before falling from a lower end portion is photographed.
3 and 4, it can be observed that a substantial portion of the water droplets discharged from the end of the thin tube has wrapped around the outer periphery of the thin tube.
　１　撥水性周面を備えた金属製細管（円筒状めっき膜複合体）
　２　第一の貴金属めっき薄膜層
　３　卑金属めっき厚膜層
　４　表面に凹凸が形成された卑金属めっき薄膜層
　５　第二の貴金属めっき薄膜層
　６　自己組織化単分子膜

                                                                        
                                                      1 Metal tube with water-repellent peripheral surface (cylindrical plating film composite)
2 First noble metal plating thin film layer 3 Base metal plating thick film layer 4 Base metal plating thin film layer with irregularities formed on the surface 5 Second noble metal plating thin film layer 6 Self-assembled monolayer


Claims (8)

  1. 　内周側から順に、第一の管状貴金属めっき層、少なくとも一方の端部の近傍領域の外周面に凹凸を持つ粗面が形成された管状卑金属めっき層、そして上記の管状卑金属めっき層の粗面が形成された領域の外周面に凹凸を備えた粗面を持つ第二の管状貴金属めっき層を含む金属製細管であって、第二の管状貴金属めっき層の凹凸を持つ粗面の外周面に撥水性の自己組織化単分子膜が形成されている、端部の近傍領域に撥水性外周面を備えた金属製細管。 In order from the inner peripheral side, a first tubular noble metal plating layer, a tubular base metal plating layer in which a rough surface having irregularities is formed on an outer peripheral surface in a region near at least one end, and a rough surface of the above tubular base metal plating layer Is a metal thin tube including a second tubular noble metal plating layer having a rough surface with irregularities on the outer peripheral surface of the region where is formed, the outer peripheral surface of the rough surface with irregularities of the second tubular noble metal plating layer A thin metal tube having a water-repellent outer peripheral surface in a region near an end, on which a water-repellent self-assembled monolayer is formed.
  2. 　上記の管状卑金属めっき層が、内周側の管状卑金属めっき厚膜層と、その外周側に形成された少なくとも一方の端部の近傍領域の外周面に凹凸を持つ粗面を備える管状卑金属めっき薄膜層を含む請求項１に記載の金属製細管。 The above-mentioned tubular base metal plating layer, a tubular base metal plating thick film layer on the inner peripheral side, and a tubular base metal plating thin film having a rough surface having irregularities on an outer peripheral surface in a region near at least one end formed on the outer peripheral side thereof The metal tubule according to claim 1, comprising a layer.
  3. 　撥水性の自己組織化単分子膜が、管状卑金属めっき層の凹凸を持つ粗面が形成された領域に接する端面も被覆するように形成されている請求項１に記載の金属製細管。 2. The thin metal tube according to claim 1, wherein the water-repellent self-assembled monomolecular film is formed so as to cover an end surface of the tubular base metal plating layer which is in contact with a region having a rough surface having irregularities.
  4. 　撥水性の自己組織化単分子膜が、管状卑金属めっき層の凹凸を持つ粗面が形成された領域の近傍の端面、そしてその端面に続く第一の管状貴金属めっき層の内周面の少なくとも一部を被覆するように形成されている請求項１に記載の金属製細管。 The water-repellent self-assembled monolayer has at least one of an end face near the region where the rough surface having irregularities of the tubular base metal plating layer is formed, and at least one inner peripheral face of the first tubular noble metal plating layer following the end face. The thin metal tube according to claim 1, wherein the thin metal tube is formed so as to cover the portion.
  5. 　第一の管状貴金属めっき層が金めっき層である請求項１に記載の金属製細管。 The thin metal tube according to claim 1, wherein the first tubular noble metal plating layer is a gold plating layer.
  6. 　管状卑金属めっき層がニッケルめっき層である請求項１に記載の金属製細管。 2. The thin metal tube according to claim 1, wherein the tubular base metal plating layer is a nickel plating layer.
  7. 　ミクロピペットもしくはミクロシリンジである請求項１に記載の金属製細管。 2. The thin metal tube according to claim 1, which is a micropipette or a microsyringe.
  8. 　芯材の外周面に第一の貴金属めっき薄膜層を形成する工程、この貴金属めっき薄膜層の外周面に卑金属めっき厚膜層を形成する工程、これらの工程により形成された貴金属めっき薄膜層と卑金属めっき厚膜層の複合層から前記芯材を除去して円筒状めっき複合体を得る工程、この円筒状めっき複合体の卑金属めっき厚膜層の外周面に、少なくとも一方の端部の近傍領域に凹凸を備える粗面を持つ卑金属めっき薄膜層を形成する工程、この卑金属めっき薄膜層の粗面を持つ領域の外周面を第二の貴金属めっき薄膜層で被覆することにより、当該領域に凹凸表面を備える粗面を持つ貴金属めっき薄膜層を形成する工程、そして、この貴金属めっき薄膜層の粗面を持つ領域の外周面に撥水性の自己組織化単分子膜を形成する工程を含む請求項１に記載の端部の近傍領域に撥水性外周面を備えた金属製細管を製造する方法。 A step of forming a first noble metal plating thin film layer on the outer peripheral surface of the core material, a step of forming a base metal plating thick film layer on the outer peripheral surface of the noble metal plating thin film layer, a noble metal plating thin film layer formed by these steps and a base metal Removing the core material from the composite layer of the plating thick film layer to obtain a cylindrical plating composite, on the outer peripheral surface of the base metal plating thick film layer of the cylindrical plating composite, in a region near at least one end; Forming a base metal plating thin film layer having a rough surface with irregularities, by coating the outer peripheral surface of the region having the rough surface of the base metal plating thin film layer with a second noble metal plating thin film layer, thereby forming an uneven surface in the region; 2. The method according to claim 1, further comprising: forming a noble metal plating thin film layer having a rough surface provided thereon; and forming a water-repellent self-assembled monomolecular film on an outer peripheral surface of a region having a rough surface of the noble metal plating thin film layer. Method of producing a metal tubular having a water repellent outer peripheral surface in the vicinity region of an end portion of the mounting.
PCT/JP2019/027871 2018-07-13 2019-07-16 Metal capillary provided in end portion with water-repellent outer circumferential surface WO2020013344A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002256446A (en) * 2001-03-06 2002-09-11 Hitachi Ltd Functional copper base-material and heat exchanger tube
JP2004115838A (en) * 2002-09-24 2004-04-15 Optical Forming Kk Production method for electroformed pipe, electroformed pipe, and fine wire rod for producing electroformed pipe
JP2010504428A (en) * 2006-09-20 2010-02-12 ザ クイーンズ ユニバーシティ オブ ベルファスト Method for coating a metal article with a surface having controlled wettability
JP2017125224A (en) * 2016-01-12 2017-07-20 仲山貴金属鍍金株式会社 Metal tube and manufacturing method therefor
WO2018131709A1 (en) * 2017-01-16 2018-07-19 仲山貴金属鍍金株式会社 Base member having increased surface hydrophobicity or hydrophilicity

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002256446A (en) * 2001-03-06 2002-09-11 Hitachi Ltd Functional copper base-material and heat exchanger tube
JP2004115838A (en) * 2002-09-24 2004-04-15 Optical Forming Kk Production method for electroformed pipe, electroformed pipe, and fine wire rod for producing electroformed pipe
JP2010504428A (en) * 2006-09-20 2010-02-12 ザ クイーンズ ユニバーシティ オブ ベルファスト Method for coating a metal article with a surface having controlled wettability
JP2017125224A (en) * 2016-01-12 2017-07-20 仲山貴金属鍍金株式会社 Metal tube and manufacturing method therefor
WO2018131709A1 (en) * 2017-01-16 2018-07-19 仲山貴金属鍍金株式会社 Base member having increased surface hydrophobicity or hydrophilicity

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