WO2016088395A1 - Liquide de nickelage, procédé de fabrication de fil revêtu de microparticules solides, et fil revêtu de microparticules solides - Google Patents

Liquide de nickelage, procédé de fabrication de fil revêtu de microparticules solides, et fil revêtu de microparticules solides Download PDF

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Publication number
WO2016088395A1
WO2016088395A1 PCT/JP2015/066497 JP2015066497W WO2016088395A1 WO 2016088395 A1 WO2016088395 A1 WO 2016088395A1 JP 2015066497 W JP2015066497 W JP 2015066497W WO 2016088395 A1 WO2016088395 A1 WO 2016088395A1
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Prior art keywords
solid fine
wire
nickel plating
fine particles
fine particle
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PCT/JP2015/066497
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English (en)
Japanese (ja)
Inventor
一之 岸
秀雄 三井
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株式会社ファシリティ
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Priority to DE112015003772.1T priority Critical patent/DE112015003772B4/de
Priority to KR1020167021051A priority patent/KR101734454B1/ko
Priority to CN201580004995.1A priority patent/CN106414807B/zh
Publication of WO2016088395A1 publication Critical patent/WO2016088395A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
    • B24D3/06—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D61/00—Tools for sawing machines or sawing devices; Clamping devices for these tools
    • B23D61/18—Sawing tools of special type, e.g. wire saw strands, saw blades or saw wire equipped with diamonds or other abrasive particles in selected individual positions
    • B23D61/185—Saw wires; Saw cables; Twisted saw strips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D65/00—Making tools for sawing machines or sawing devices for use in cutting any kind of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B27/00—Other grinding machines or devices
    • B24B27/06—Grinders for cutting-off
    • B24B27/0633—Grinders for cutting-off using a cutting wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
    • B24D18/0018—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for by electrolytic deposition
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C25D3/40—Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current

Definitions

  • the present invention relates to a nickel plating solution used for manufacturing a solid fine particle-attached wire in which solid fine particles such as diamond are dispersed on the wire surface, a method for producing the solid fine particle-attached wire, and the solid fine particle-attached wire.
  • Solid particle adhesion wire made by fixing solid particles such as diamond to the outer peripheral surface of the wire is hard and brittle like silicon wafers for solar cells, silicon wafers for semiconductors, sapphire in LED applications, ceramics and stones. Suitable for cutting highly difficult-to-process materials.
  • a tool wire saw
  • Patent Document 1 relates to a solid fine particle-attached wire formed by fixing solid fine particles on the outer peripheral surface of a wire.
  • a solid fine particle-containing electrolytic nickel plating layer in which solid fine particles with an inorganic coat layer subjected to a surface modification treatment are dispersed on the surface of the wire, and the surface of the solid fine particle-containing electrolytic nickel plating layer is overlaid.
  • a technique including a coated nickel plating layer is disclosed.
  • An object is to provide a nickel plating solution, a method for producing a fixed fine particle-attached wire using the nickel plating solution, and the solid fine particle-attached wire.
  • the inventors of the present invention adopted a nickel plating solution described below, a method for producing a solid fine particle-attached wire, and the solid fine particle-attached wire.
  • the nickel plating solution according to the present invention is a nickel plating solution for forming an electrolytic nickel plating layer containing solid fine particles dispersed on the wire surface, and is a solid with an inorganic coating layer subjected to a surface modification treatment. It contains fine particles and polyamines as a dispersant.
  • the polyamine is preferably a polyethyleneimine having a number average molecular weight of 800 to 2,000,000.
  • the concentration of the polyamines is preferably 1 mg / L to 100 mg / L.
  • the solid fine particles with an inorganic coat layer are preferably those obtained by modifying the particle surface to a charged surface with a surface modifier.
  • the surface modifier preferably contains one or more of any one of amine-based, non-ionic and cationic surfactants.
  • the surface modifier preferably contains an alcohol amine and a nonionic surfactant.
  • the solid fine particles preferably have a particle size of 0.01 ⁇ m to 100 ⁇ m.
  • the solid fine particles with an inorganic coat layer may be one or more selected from diamond particles with a palladium coat layer, diamond particles with a nickel coat layer, and diamond particles with a titanium coat layer. Preferably there is.
  • the manufacturing method of the solid fine particle adhesion wire which concerns on this invention is a manufacturing method of the solid fine particle adhesion wire which fixes solid fine particles to the outer peripheral surface of a wire, Comprising: The following process a and process b is included.
  • Step a Using the above-described nickel plating solution, nickel is deposited on the surface of the wire by electrolytic plating, and at the same time, composite plating for attaching the solid fine particles with the inorganic coat layer is performed, and the solid fine particle-containing nickel plating is applied to the surface of the wire. Forming a layer; Step b. Forming an overcoat nickel plating layer on the solid fine particle-containing nickel plating layer on the wire surface;
  • the wire preferably includes an inorganic protective layer on the surface thereof.
  • the wire preferably has a diameter of 0.02 mm to 3.0 mm.
  • Solid particulate adhering wire The solid particulate adhering wire according to the present invention is obtained by using the above-described method for producing a solid particulate adhering wire.
  • the solid fine particle-attached wire according to the present invention is preferably one in which 10 to 100 solid fine particles with an inorganic coat layer having a particle size of 0.01 to 100 ⁇ m are attached within a length range of 500 ⁇ m of the wire. .
  • the nickel plating solution according to the present invention is a nickel plating solution for forming an electrolytic nickel plating layer containing dispersed solid fine particles on the wire surface, and the solid fine particles with an inorganic coat layer subjected to surface modification treatment,
  • the polyamines as the agent, it is possible to avoid the aggregation of the solid fine particles on the wire surface and form an electrolytic nickel plating layer in which the solid fine particles are more uniformly dispersed. Therefore, the cutting performance at the time of using a solid fine particle adhesion wire as a wire saw can be improved greatly.
  • FIG. 1 It is a mimetic diagram of a solid particulate adhesion wire section concerning the present invention. It is a photograph which shows the state of the wire surface which formed the solid nickel containing electrolytic nickel plating layer using the nickel plating liquid of polyethyleneimine density
  • FIG. It is a photograph which shows the state of the wire surface which formed the solid nickel containing electrolytic nickel plating layer using the nickel plating solution of polyethyleneimine density
  • FIG. It is a photograph which shows the state of the wire surface which formed the solid nickel containing electrolytic nickel plating layer using the nickel plating liquid of polyethyleneimine density
  • the nickel plating solution according to the present invention is a nickel plating solution for forming an electrolytic nickel plating layer containing solid fine particles dispersed on the wire surface.
  • the nickel plating solution according to the present invention is characterized in that the plating solution containing a nickel component contains at least solid fine particles with an inorganic coat layer subjected to a surface modification treatment and polyamines as a dispersant.
  • the nickel plating solution according to the present invention is a pure nickel plating solution and a commercially available electrolytic nickel plating solution such as a nickel alloy (nickel-based alloy such as nickel-phosphorus, nickel-cobalt, nickel-zinc) plating solution.
  • a suspension of solid fine particles with an inorganic coat layer that has been surface-modified by adding polyamines can also be used as a dispersant by constructing a Watt bath, a sulfamic acid bath, etc. that are applied to nickel plating.
  • a material obtained by suspending solid fine particles with an inorganic coat layer that has been subjected to surface modification treatment with the addition of polyamines may be used.
  • the nickel plating solution at this time is not particularly limited except that polyamines are used as a dispersant, and it is possible to adopt a bath composition and electrolytic conditions that allow smooth nickel plating.
  • a bath composition and electrolytic conditions that allow smooth nickel plating.
  • several nickel plating baths and plating conditions are listed below.
  • nickel sulfamic acid nickel plating bath nickel sulfamate tetrahydrate 200 g / L to 800 g / L, nickel chloride hexahydrate 1 g / L to 10 g / L, boric acid 20 g / L
  • a nickel plating composition of L to 50 g / L and pH of 3 to 5 is employed.
  • nickel sulfate heptahydrate is 200 g / L to 500 g / L
  • nickel chloride heptahydrate is 10 g / L to 100 g / L
  • boric acid is 20 g / L.
  • a nickel plating composition of L to 50 g / L and pH of 3 to 5 is employed.
  • polyethyleneimine, modified polyethyleneimine, or the like can be used as the polyamine as the dispersant.
  • polyethyleneimine having a number average molecular weight of 800 to 2,000,000 is preferably used.
  • the solid fine particles can be uniformly dispersed on the wire surface during the electroplating in the production method of the solid fine particle-attached wire described below.
  • the amount of solid fine particles with an inorganic coat layer adhering to the solid fine particle adhering wire in proportion to the amount of solid fine particles with an inorganic coat layer in the nickel plating solution is obtained.
  • the concentration of the polyamines used as a dispersant in the nickel plating solution is preferably 1 mg / L to 100 mg / L.
  • the concentration of polyamines in the nickel plating solution is less than 1 mg / L, the effect as a dispersant is less likely to appear during electroplating, and solid fine particles on the wire surface compared to the case where no polyamines are added at all. This is because no change is observed in the aggregation state.
  • the concentration of polyamines in the nickel plating solution exceeds 100 mg / L, cracks may occur in the formed solid fine particle-containing electrolytic nickel plating layer.
  • the solid fine particles with an inorganic coating layer subjected to the surface modification treatment used in the nickel plating solution according to the present invention include, for example, cerium oxide, silicon oxide (quartz, fused silica, etc.), alumina, silicon carbide, silicon nitride as a core material. Fine particles such as zirconium oxide, diamond, and Teflon (registered trademark) can be used. However, the said core material is not limited to what was enumerated in these, According to the use of the solid fine particle adhesion wire manufactured using the said nickel plating solution, it can select suitably. In particular, when using a solid fine particle-attached wire produced using the nickel plating solution as a wire saw for cutting a silicon wafer or the like, it is preferable to employ diamond particles.
  • the solid fine particles having a particle diameter of 0.01 ⁇ m to 100 ⁇ m are preferably used.
  • the particle size of the solid fine particles is less than 0.01 ⁇ m, the surface of the solid fine particle attached wire produced using the nickel plating solution becomes too smooth, not only for wire saw use, but also for other uses, Since the significance of attaching solid fine particles to the wire is lost, it is not preferable.
  • the particle diameter of the solid fine particles exceeds 100 ⁇ m, even if a wire having a diameter of 0.8 mm is used as a wire for forming the solid fine particle-containing electrolytic nickel plating layer with the nickel plating solution, the wire surface is uniform.
  • the particle diameter is 0.08 mm to 0.2 mm for the wire.
  • the use of solid fine particles of 4 to 40 ⁇ m shows good cutting performance suitable for wire saw applications, and the solid fine particles adhering to the wire surface are less likely to fall off during cutting, thus extending the life of the wire saw. Since it becomes possible, it is more preferable.
  • the inorganic coat layer formed on the surface of the solid fine particles serving as the core material is composed of a metal component.
  • the constituent components of the inorganic coat layer can be appropriately selected and used according to the use of the solid fine particle-attached wire produced using the nickel plating solution.
  • Specific examples of the solid fine particles with an inorganic coat layer in the present invention include solid fine particles with a palladium coat layer, solid fine particles with a nickel coat layer, and solid fine particles with a titanium coat layer.
  • a solid fine particle-attached wire manufactured using the nickel plating solution is used as a wire saw for cutting a silicon wafer or the like, diamond particles with a palladium coat layer, diamond with a nickel coat layer are used as solid fine particles with an inorganic coat layer.
  • the solid fine particles with an inorganic coat layer provided with these inorganic coat layers have good wettability with the precipitation component of nickel or nickel alloy formed using the nickel plating solution, and good adhesion can be obtained.
  • the solid fine particles with an inorganic coat layer are preferably those obtained by coating the surface of the solid fine particles with palladium by the following method.
  • the first palladium coating method is as follows: “After palladium and tin are co-deposited on the surface of the solid fine particles, only the tin on the surface of the solid fine particles is decomposed and removed, so that only palladium exists on the surface of the solid fine particles. It is a method to make it a state. " This method will be described with a specific example.
  • a solution containing tin and palladium a solution containing a palladium / tin colloidal catalyst as a main component can be used. When solid fine particles are immersed in such a solution, palladium / tin colloid is adsorbed on the surface of the solid fine particles.
  • the amount of palladium adsorbed at this time is preferably 0.1 mg to 20 mg per 1 g of solid fine particles.
  • the palladium adsorption amount is less than 0.1 mg per 1 g of solid fine particles, the amount of palladium adsorption on the particle surface of the solid fine particles is small, and the precipitation component of nickel or nickel alloy formed using the nickel plating solution according to the present invention This is not preferable because the wettability cannot be sufficiently improved and good adhesion cannot be obtained.
  • the palladium adsorption amount exceeds 20 mg per 1 g of the solid fine particles, the eutectoid effect of nickel and the solid fine particles is saturated and cannot be improved.
  • a more preferable amount of palladium adsorbed is 0.1 mg per 1 g of the solid fine particles. ⁇ 10 mg.
  • the solid fine particles having palladium / tin colloids adsorbed on the particle surface are brought into contact with an acid such as chlorine, sulfuric acid, borohydrofluoric acid, etc. to dissolve and remove the tin component. Precipitate.
  • an acid such as chlorine, sulfuric acid, borohydrofluoric acid, etc.
  • a palladium coat layer is formed on the surface of the solid fine particles.
  • the second palladium coating method is as follows: “Solid fine particles are immersed in a tin solution for a predetermined time to deposit tin on the surface of the solid fine particles, and then immersed in a palladium solution for a predetermined time to perform a substitution reaction between tin and palladium. A method of using this method to deposit palladium on the particle surface.
  • chlorine, sulfuric acid, borofluoric acid, carboxylic acid in order to reliably remove tin contained in the palladium coat layer, chlorine, sulfuric acid, borofluoric acid, carboxylic acid, It can also be removed using an acidic solution such as oxycarboxylic acid or aromatic carboxylic acid.
  • the first palladium coating method and the second palladium coating method are merely examples, and among the solid fine particles with inorganic coat layer used in the present invention, the solid fine particles with palladium coat layer cover the surface of the solid fine particles with the palladium coat layer. As long as it is coated with, it is not limited to these methods.
  • the solid fine particles with an inorganic coat layer are subjected to surface modification treatment.
  • solid fine particles with an inorganic coat layer are attached to the surface of the wire, and simultaneously from nickel ions having a positive charge. A nickel component is deposited. Therefore, it is necessary to use a surface modifier used in the surface modification treatment that can stabilize the surface of the solid fine particles with an inorganic coat layer by imparting a positive polarity.
  • a surface modifier it is preferable to use one containing an amine surfactant, a nonionic surfactant or a cationic surfactant, and among them, a nonion containing alcohol amines. It is preferable to use a system surfactant.
  • the surface modifier and the solid fine particles are brought into contact with each other for a predetermined time, whereby the surface of the solid fine particles with an inorganic coat layer is efficiently charged to the positive electrode, and the positive electrode is charged. This is because stabilization can be achieved. In this way, the surface of the solid fine particles with an inorganic coat layer is subjected to a surface modification treatment.
  • an optimum method is selected from the method of immersing the solid fine particles in the surface treatment agent, the method of spraying the surface treatment agent on the surface of the solid fine particles, and the like. Can be implemented. If the dipping method is adopted, the solid fine particles are put into a treatment tank containing a surface modifier, and the dipping process is performed for a predetermined time while stirring. When the treatment for a predetermined time is completed, the solid fine particles are separated and collected from the treatment tank, washed with water, and dried.
  • the content of the solid fine particles with the inorganic coating layer in the nickel plating solution according to the present invention described above is arbitrarily selected in consideration of the relationship with the amount of solid fine particles co-deposited with nickel on the surface of the wire. It is possible.
  • the solid fine particle content is preferably about 0.1 g / L to 40 g / L depending on the type of the object to be cut. This is because if the solid fine particle content is less than 0.1 g / L, the wire saw does not have good cutting performance.
  • the solid fine particle content exceeds 40 g / L, the amount of solid fine particles adhering to the wire surface becomes excessive, and it becomes difficult to uniformly adhere the solid fine particles to the wire surface.
  • the solid fine particles are formed on the wire surface.
  • the electrolytic nickel plating layer containing the dispersion it is possible to avoid the aggregation of the solid fine particles on the wire surface, and to form the electrolytic nickel plating layer in which the solid fine particles are more uniformly dispersed. Therefore, the cutting performance at the time of using a solid fine particle adhesion wire as a wire saw can be improved greatly.
  • the wire used in the method for producing a solid fine particle-attached wire according to the present invention is not particularly limited as long as the surface can be electroplated and has a certain strength, and is appropriately selected according to the intended use. can do.
  • Examples of such wires include steel wires such as piano wires, tungsten wires, molybdenum wires, and stainless steel wires.
  • the diameter of the wire which is the core material of the solid fine particle-attached wire, should not be limited if originally intended, and may be selected as appropriate according to the application. However, considering that most of the applications of the solid fine particle-attached wire are “wire saws”, the diameter of the wire is preferably 0.02 mm to 3.0 mm. In the case of a solid fine particle-attached wire that functions as a wire saw, if the wire diameter is less than 0.02 mm, it is difficult to efficiently attach the solid fine particles with an inorganic coat layer to the wire surface. On the other hand, since the upper limit of the diameter of this wire changes with uses, it is defined as a temporary standard.
  • the upper limit is 0.8 mm. If the diameter of the wire exceeds 0.8 mm, it is not always necessary to use a wire saw from the viewpoint of cutting accuracy of the object to be cut.
  • the solid fine particle-attached wire is used for cutting a silicon wafer of a solar cell, it is best to use a wire having a diameter of 0.06 mm to 0.23 mm to meet the market demand.
  • 3.0 mm is an upper limit. This is because if the diameter of the wire exceeds 3.0 mm, the flexibility as the wire is lost and the handling becomes difficult.
  • the degreasing method at this time is not particularly limited, and for example, acid soaking, solvent degreasing, emulsifier degreasing, alkaline degreasing and the like can be applied. Furthermore, it is also possible to apply electrolytic degreasing as required.
  • the said wire used in the manufacturing method of the solid particulate adhesion wire of this invention it is preferable to use what equips the surface with an inorganic protective layer.
  • the inorganic protective layer By the presence of the inorganic protective layer on the surface of the wire, it is possible to prevent the occurrence of microcracks on the wire surface during the processing, the occurrence of disconnection, and the corrosion of the wire.
  • the type of the inorganic protective layer it becomes possible to stabilize the adhesion state of solid fine particles described later.
  • nickel, nickel alloy (Ni—Co, Ni—Sn, Ni—Zn), Cu, copper alloy (Cu—Zn, Cu—Sn), etc. can be used.
  • the inorganic protective layer made of nickel or nickel alloy is preferably formed using a so-called “strike plating method”.
  • This strike plating uses a low ion concentration electrolytic solution to perform a short plating process at a high current density to form a thin plating layer having a thickness of 1.0 ⁇ m or less.
  • a current supply method at this time it is of course possible to perform plating with a simple direct current, but in order to prevent deterioration in quality due to the use of a high current density, a “pulse” is repeatedly applied between an energized state and a current stopped state. It is also preferable to employ the “plating method”.
  • pulse waveform When employing pulse plating, there is no particular limitation on the pulse waveform, and a rectangular wave, a triangular wave, or the like can be used.
  • the rectification method is not limited, and half-wave rectification and full-wave rectification can be used. It is possible to employ conditions such as a frequency of 200 Hz to 2000 Hz, a duty ratio (on: 20, off: 80), and a current density of 3 A / dm 2 to 10 A / dm 2 .
  • nickel strike plating it is possible to use a sulfamic acid-based nickel plating bath and a watt bath described later.
  • copper cyanide strike plating copper cyanide is 20 g / L to 35 g / L
  • sodium cyanide is 37 g / L to 60 g / L
  • potassium hydroxide is 3 g / L to 5 g / L
  • Rochelle salt is 10 g / L.
  • An electrolytic solution containing L to 20 g / L can be used.
  • an electrolytic solution containing 16 g / L of copper pyrophosphate, 120 g / L of potassium pyrophosphate, and 10 g / L of potassium oxalate can be used.
  • the manufacturing method of the solid fine particle adhesion wire which concerns on this invention is forming the solid fine particle containing electrolytic nickel plating layer and the overcoat nickel plating layer on the surface of a wire by performing the following process a and process b. Features. Hereinafter, each step will be described.
  • Step a In this step, as described in detail above, a wire is obtained by electrolytic plating using a polyamine as a dispersing agent and a nickel plating solution containing solid fine particles with an inorganic coat layer subjected to surface modification treatment. At the same time as nickel is deposited on the surface, composite plating is performed to deposit solid fine particles with an inorganic coat layer, thereby forming an electrolytic nickel plating layer containing solid fine particles on the surface of the wire.
  • the method for producing a solid fine particle-attached wire according to the present invention uses a plating solution in which solid fine particles with an inorganic coat layer subjected to surface modification treatment are suspended in a nickel plating solution containing polyamines as a dispersant.
  • nickel and solid fine particles can be co-deposited on the surface of the wire.
  • the number of the solid fine particles is less than 10, it is not preferable because cutting performance as a wire saw is deteriorated.
  • Step b In this step, an overcoat nickel plating layer is further formed on the solid fine particle-containing electrolytic nickel plating layer formed on the wire surface on the surface of the solid fine particle-containing electrolytic nickel plating layer obtained in step a.
  • the nickel plating method applied here is preferably an electrolytic plating method from the viewpoint of production speed.
  • the plating solution used in this step b is preferably composed of a pure nickel plating solution or a nickel alloy (nickel-based alloy such as nickel-phosphorus, nickel-cobalt, nickel-zinc) plating solution.
  • the plating solution used in the step b is not limited to this, and a commercially available nickel plating bath may be used. As detailed in the above-mentioned “nickel plating solution”, You may use what prepared the sulfamic acid bath etc. itself.
  • the above-mentioned wire on which the solid fine particle-containing electrolytic nickel plating layer is formed is immersed in a nickel plating solution having a liquid temperature of 30 ° C. to 60 ° C., and the wire is polarized to the cathode, so that the solid fine particle-containing electrolytic nickel plating layer An overcoat nickel plating layer having a desired thickness is formed on the substrate.
  • a nickel plating solution having a liquid temperature of 30 ° C. to 60 ° C.
  • the wire is polarized to the cathode, so that the solid fine particle-containing electrolytic nickel plating layer
  • An overcoat nickel plating layer having a desired thickness is formed on the substrate.
  • the temperature of the nickel plating solution is less than 30 ° C., the amount of saturated nickel that can be contained in the plating solution is reduced, the plating rate is reduced, and the industrial productivity is reduced.
  • the smoothness of the surface of the overcoated nickel plating layer tends to decrease, which is not preferable.
  • the overcoat nickel plating layer formed in this step b is provided on the outer surface of the solid fine particle-containing electrolytic nickel plating layer, and is located on the outermost layer of the solid fine particle-attached wire. Therefore, the overcoat nickel plating layer can effectively prevent the solid fine particles included in the solid fine particle-containing electrolytic nickel plating layer from falling off.
  • the overcoat nickel plating layer preferably has a thickness of 0.1 ⁇ m to 40 ⁇ m. When the thickness of the overcoat nickel plating layer is less than 0.1 ⁇ m, the solid fine particles contained in the solid fine particle-containing electrolytic nickel plating layer, which occurs during the handling or cutting operation of the solid fine particle adhesion wire, can be effectively removed. It cannot be prevented.
  • the thickness of the overcoat nickel plating exceeds 40 ⁇ m by employing the electrolytic plating method, current concentration occurs at the top of the diamond particle, and abnormal precipitation of nickel occurs at the current concentration point.
  • the plating thickness at the top of the particle increases. Assuming a solid fine particle-attached wire to be used as a wire saw at this time, in the state where the plating thickness of the top part of the diamond particle is increased, it is difficult for the top part of the diamond to be exposed immediately after the start of use as a wire saw. Since the initial cutting performance is lowered, it is not preferable.
  • the thickness of the overcoat nickel plating layer is 2 ⁇ m to 4 ⁇ m.
  • the overcoat nickel plating layer preferably has a thickness of 0.1 ⁇ m to 40 ⁇ m.
  • the thickness of the overcoat nickel plating layer is 2 ⁇ m, it is possible to almost completely prevent the solid fine particles contained in the solid fine particle-containing electrolytic nickel plating layer from falling off during handling or cutting operation of the solid fine particle adhesion wire.
  • the thickness of the overcoat nickel plating layer exceeds 4 ⁇ m, the effect of preventing the solid fine particles contained in the solid nickel-containing electrolytic nickel plating layer is already saturated, rather, the current concentration at the top of the diamond particles This is because the process management tends to be complicated.
  • the thickness of the overcoat nickel plating layer 6 is measured at a location where the solid fine particles 4 do not exist in the overcoat nickel plating layer 6.
  • the solid fine particle-attached wire according to the present invention is a solid fine particle-attached wire obtained by the above-described method for producing a solid fine particle-attached wire according to the present invention, using the nickel plating solution according to the present invention described above in detail.
  • the solid fine particle-attached wire according to the present invention includes a “solid fine particle-containing electrolytic nickel plating layer” in which a “solid fine particle with an inorganic coat layer subjected to surface modification treatment” is dispersed on the outer peripheral surface of the wire, An “overcoat nickel plating layer” is provided on the surface of the solid nickel-containing electrolytic nickel plating layer.
  • a “solid fine particle-containing electrolytic nickel plating layer” in which a “solid fine particle with an inorganic coat layer subjected to surface modification treatment” is dispersed on the outer peripheral surface of the wire.
  • An “overcoat nickel plating layer” is provided on the surface of the solid nickel-containing electrolytic nickel plating layer.
  • Solid fine particle-containing electrolytic nickel plating layer This solid fine particle-containing electrolytic nickel plating layer directly contacts and coats the surface of the wire, and contains solid fine particles with an inorganic coating layer dispersed in the electrolytic nickel plating layer. Yes. That is, the nickel component plays a role as a binder for fixing the solid fine particles with the inorganic coat layer to the wire surface.
  • the nickel component contained in the solid fine particle-containing electrolytic nickel plating layer is not just a surface coating, but has a wire and good wettability and exhibits chemical affinity. Therefore, the electrolytic nickel layer provided on the wire surface by an electrolytic method has good adhesion.
  • the solid fine particles with an inorganic coating layer contained in the solid fine particle-containing electrolytic nickel plating layer are, for example, cerium oxide, silicon oxide (quartz, quartz) as a core material, as described in detail in the above-mentioned “form of nickel plating solution”. Fine particles such as fused silica, alumina, silicon carbide, silicon nitride, zirconium oxide, diamond, Teflon (registered trademark), and the like can be used.
  • the inorganic coating layer formed on the surface of the solid fine particles is composed of a metal component, and may be appropriately selected and used depending on the use of the solid fine particle-attached wire produced using the nickel plating solution. Is possible.
  • the solid fine particles with an inorganic coating layer contained in the solid fine particle-containing electrolytic nickel plating layer of the solid fine particle-attached wire in the present invention are specifically diamond particles with a palladium coat layer, diamond particles with a nickel coat layer, diamond particles with a titanium coat layer It is preferable to employ
  • the solid fine particle-containing electrolytic nickel plating layer of the solid fine particle-attached wire according to the present invention comprises solid fine particles with an inorganic coat layer subjected to surface modification treatment, and polyamines as a dispersant. Since it is formed by the electroplating method using the contained nickel plating solution, the solid fine particles on the wire surface are hardly agglomerated and electrolyzed in a state in which the solid fine particles are more uniformly dispersed than in the past. It is fixed by a nickel plating layer. Therefore, the cutting performance at the time of using the said solid fine particle adhesion wire as a wire saw can be improved greatly.
  • the solid fine particle-containing electrolytic nickel plating layer is preferably one in which 10 to 100 solid fine particles with an inorganic coat layer having a particle diameter of 0.01 to 100 ⁇ m are attached within a length range of 500 ⁇ m of the wire. .
  • the solid nickel-containing electrolytic nickel plating layer has 10 to 100 solid fine particles with an inorganic coat layer attached thereto, so that the solid fine particles are dispersed almost appropriately without agglomeration.
  • a solid fine particle-containing electrolytic nickel plating layer can be formed. Therefore, when it is used as a wire saw, the solid fine particles are less likely to fall off, and high cutting performance can be maintained.
  • Overcoat nickel plating layer This overcoat nickel plating layer is provided on the surface of the above-mentioned solid fine particle-containing electrolytic nickel plating layer containing solid fine particles, and constitutes the outermost layer of the solid fine particle-attached wire. Therefore, the overcoat nickel plating layer functions to prevent the solid fine particles contained in the solid fine particle-containing electrolytic nickel plating layer from falling off.
  • the “overcoat nickel plating layer” mentioned here is a pure nickel plating solution, a nickel alloy (nickel-phosphorus, nickel-cobalt, nickel-zinc) as described in the “form of manufacturing method of solid fine particle-attached wire”. It is preferable to use a nickel-based alloy) plating solution.
  • the nickel component contained in this “overcoat nickel plating layer” is not limited to a mere surface coating, and exhibits good wettability with the above-mentioned “solid nickel-containing electrolytic nickel plating layer”, and the foundation is made of solid fine particles. Even if there are irregularities, the film is thin and uniform with good throwing power.
  • Example 1 a steel wire wire having a diameter of 0.35 mm manufactured by Japan Fine Steel Co., Ltd. was used as the wire. Prior to the formation of the solid fine particle-containing electrolytic nickel plating layer in step c, which will be described later, the wire was degreased and then pretreated by immersion in 10% sulfuric acid. Thereafter, nickel strike plating was applied to the surface of the wire to form an inorganic protective layer having a thickness of 0.5 ⁇ m.
  • the nickel strike plating at this time uses an electrolyte containing 240 g / L of nickel chloride and 125 g / L of hydrochloric acid, the pulse waveform is a short wave, the frequency is 1000 Hz, the duty ratio (on: 20, off: 80), the current Pulse electrolysis conditions with a density of 2.5 A / dm 2 were employed. Similar wires are used in other examples and comparative examples.
  • Example 1 Solid fine particles with inorganic coat layer:
  • diamond particles (average particle size 35 ⁇ m) having a particle size in the range of 30 ⁇ m to 40 ⁇ m were used as the solid fine particles. Then, an inorganic coat layer was formed on the surface of the diamond particles.
  • Example 1 as a method for forming the inorganic coating layer, a method of depositing palladium and tin on the surface of diamond particles using a solution containing a palladium-tin colloidal catalyst as a main component was employed. Specifically, in Example 1, a solution having a palladium concentration of 0.1 g / L, a tin concentration of 2 g / L, and 40 ° C. was used.
  • the particle diameter of the “diamond particles with a palladium coat layer” was in the range of 30 ⁇ m to 40 ⁇ m (average particle diameter of 35 ⁇ m).
  • the surface modification treatment of the obtained “diamond particles with a palladium coat layer” was performed using a solution containing a nonionic surfactant containing an alcoholamine as a surface modifier.
  • a solution of 5% by mass of 2-aminoethanol (primary amine), 1% by mass of a nonionic surfactant, and pH 10 was used.
  • “diamond particles with a palladium coat layer” are placed in the surface modifier maintained at a liquid temperature of about 30 ° C., soaked for 10 minutes, and then washed with water.
  • grains with the palladium coat layer which performed the process were obtained.
  • Example 2 and Comparative Example described later diamond particles with a palladium coat layer subjected to the same modification treatment are used.
  • Step a “diamond particle-containing electrolytic nickel plating solution” in which the above-mentioned diamond particles with a palladium coat layer are placed in an electrolytic nickel plating solution and the concentration of diamond particles with a palladium coat layer is 0.2 g / L. Got.
  • the diamond particle-containing electrolytic nickel plating solution is composed of nickel sulfamate tetrahydrate 400 g / L, nickel chloride hexahydrate 2 g / L, polyethyleneimine (number average molecular weight 70,000) 1 mg / L, and boric acid 35 g. / L, pH 4.0 nickel sulfamate plating solution was used.
  • the temperature of the diamond particle-containing electrolytic nickel plating solution is set to 65 ° C.
  • electrolysis is performed at a current density of 7.8 A / dm 2 for 30 minutes, and the above degreasing treatment is performed on the surface of the wire on which the inorganic protective layer is formed.
  • Composite plating was performed to form a “diamond particle-containing electrolytic nickel plating layer” in which diamond particles with a palladium coat layer were dispersed and contained.
  • the converted thickness of the “diamond particle-containing electrolytic nickel plating layer” was 6.2 ⁇ m.
  • Step b In step b, a nickel sulfamate plating bath of nickel sulfamate tetrahydrate 450 g / L, nickel chloride hexahydrate 3 g / L, boric acid 40 g / L, pH 4.0 is used as a plating solution. Adopted. Then, the liquid temperature of the nickel plating solution is electrolyzed for 15 minutes at 65 ° C. and a current density of 8.7 A / dm 2 , and the converted thickness is applied to the surface of the diamond particle-containing electrolytic nickel plating layer provided on the wire surface in step a. An “overcoat nickel plating layer” of 10.5 ⁇ m was formed to produce a “diamond fine particle-attached wire”.
  • FIG. 2 shows a 200 ⁇ external appearance photograph of the diamond fine particle-attached wire produced in Example 1.
  • the diamond fine particle-attached wire of Example 1 had a finished diameter value after plating and a wire diameter monitor value representing the eutectoid state of diamond of 446.9 ⁇ m. Further, an average of 32.5 diamond particles with a palladium coat layer adhered to the 500 ⁇ m length range of the diamond fine particle adhering wire.
  • Example 2 differs from Example 1 only in the concentration condition of the polyethyleneimine (number average molecular weight 70,000) in step a, and all other conditions are the same as in Example 1 to obtain a diamond fine particle-attached wire. Produced. Below, only the conditions of the process a different from Example 1 are demonstrated.
  • Example 2 the electrolytic nickel plating solution was prepared by setting the concentration of polyethyleneimine (number average molecular weight 70,000) of the nickel sulfamate plating solution in step a to 5 mg / L.
  • the other conditions such as temperature, current density, electrolysis time, etc. of the plating solution were the same as those in Example 1.
  • FIG. 3 shows a 200 ⁇ external appearance photograph of the diamond fine particle-attached wire produced in Example 2.
  • the diamond fine particle-attached wire of Example 2 had a wire diameter monitor value of 435.3 ⁇ m.
  • Example 3 is different from Example 1 only in the concentration condition of the polyethyleneimine (number average molecular weight 70,000) in step a, and all other conditions are the same as in Example 1 to obtain a diamond fine particle-attached wire. Produced. Below, only the conditions of the process a different from Example 1 are demonstrated.
  • Example 3 the electrolytic nickel plating solution was prepared by setting the concentration of polyethyleneimine (number average molecular weight 70,000) of the nickel sulfamate plating solution in step a to 10 mg / L.
  • the other conditions such as temperature, current density, electrolysis time, etc. of the plating solution were the same as those in Example 1.
  • FIG. 4 shows a 200 ⁇ external appearance photograph of the diamond fine particle-attached wire produced in Example 3.
  • the diamond fine particle-attached wire of Example 3 had a wire diameter monitor value of 415.6 ⁇ m.
  • step a only the conditions of the nickel sulfamate plating solution used in step a are different from those in Examples 1 to 3, and all other conditions are the same as those in Examples 1 to 3, and diamond fine particles are adhered. A wire was made. Only the conditions of step a, which are different from those in the first to third embodiments, will be described below.
  • the nickel sulfamate plating solution in step a did not contain polyethyleneimine.
  • the other conditions such as temperature, current density, electrolysis time, etc. of the plating solution were the same as those in Example 1.
  • FIG. 5 shows a 200 ⁇ external appearance photograph of the diamond fine particle-attached wire produced in this comparative example.
  • the diamond fine particle-attached wire of the comparative example had a wire diameter monitor value of 455.5 ⁇ m.
  • Examples 1 to 3 in which polyethyleneimine is added to the electrolytic nickel plating solution in step a and comparative examples in which polyethyleneimine is not added are wire diameter monitor values indicating the agglomeration state of diamond particles, that is, after plating. Despite the smaller outer diameter of the wire, the average number of adhered diamond particles with a palladium coat layer remained almost unchanged. From this, it can be understood that the agglomeration of the diamond-coated diamond particles on the diamond fine particle-attached wire is reduced and the dispersibility is improved. This fact can also be confirmed from FIGS. 2 to 5 showing appearance photographs of the examples and comparative examples.
  • the wire diameter monitor value decreases as the concentration of polyethyleneimine in the electrolytic nickel plating solution in step a increases. Therefore, it can be understood that the effect of the polyethyleneimine as a dispersant increases as the concentration increases.
  • the electrolytic nickel in step a is compared with the solid fine particle-attached wire according to the comparative example. It can be seen that the cutting performance of the solid fine particle-attached wires according to the respective examples using polyethyleneimine as the plating solution is drastically improved by increasing the dispersibility of the solid fine particles.
  • the nickel plating solution according to the present invention avoids agglomeration of solid fine particles adhering to the wire by using it when forming an electrolytic nickel plating layer containing solid fine particles dispersed on the wire surface.
  • An electrolytic nickel plating layer in which solid fine particles are uniformly dispersed can be formed.
  • Such a solid fine particle adhering wire can be used suitably in a manufacturing process of a solar cell, a silicon wafer for a semiconductor, and the like because it can cut a highly brittle material such as an ingot of single crystal silicon with high accuracy.
  • the excellent polishing performance of the solid fine particle-attached wire according to the present invention is suitable for various uses such as a file and a sharpening knife, and can be applied to various uses that require cutting or grinding.

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Abstract

La présente invention concerne un liquide de nickelage qui peut amener des microparticules solides telles que des microparticules de diamant à se fixer à la surface d'un fil selon une dispersion uniforme, sans amener les microparticules solides à s'agréger, un procédé de fabrication d'un fil sur lequel des microparticules solides sont fixées à l'aide du liquide de nickelage, et le fil sur lequel des microparticules solides sont fixées. Pour ce faire, un liquide de nickelage contenant une polyamine en tant qu'agent de dispersion et des microparticules solides pourvues d'une couche de revêtement inorganique appliquée grâce à un traitement de modification de surface est utilisé sous la forme d'un liquide de nickelage destiné à former une couche de nickelage électrolytique contenant des microparticules solides dispersées à la surface d'un fil.
PCT/JP2015/066497 2015-05-29 2015-06-08 Liquide de nickelage, procédé de fabrication de fil revêtu de microparticules solides, et fil revêtu de microparticules solides WO2016088395A1 (fr)

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DE112015003772.1T DE112015003772B4 (de) 2015-05-29 2015-06-08 Nickelplattierungslösung, Verfahren zur Herstellung eines mit Feststoffteilchen behafteten Drahts, und mit Feststoffteilchen behafteter Draht
KR1020167021051A KR101734454B1 (ko) 2015-05-29 2015-06-08 니켈 도금액, 및 고체 미립자 부착 와이어의 제조 방법
CN201580004995.1A CN106414807B (zh) 2015-05-29 2015-06-08 镀镍液、固体微粒附着金属线的制造方法和固体微粒附着金属线

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CN110438550A (zh) * 2019-08-14 2019-11-12 苏州韦度新材料科技有限公司 一种超锋利型金刚石线锯的制备方法及金刚石线锯
JP7501896B2 (ja) 2020-07-16 2024-06-18 奥野製薬工業株式会社 電気ニッケルめっき皮膜及びめっき液、並びに電気ニッケルめっき液を用いた電気ニッケルめっき皮膜の製造方法
CN115874246A (zh) * 2022-12-30 2023-03-31 长沙岱勒新材料科技股份有限公司 一种制备环形金钢石线锯的上砂方法及环形金刚石线锯
CN118531479A (zh) * 2024-07-23 2024-08-23 浙江求是半导体设备有限公司 电镀钨丝金刚线及其制备方法

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CN106414807A (zh) 2017-02-15
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DE112015003772T5 (de) 2017-05-11
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