WO2013039097A1

WO2013039097A1 - Wire coated with solid microparticles, and method for producing wire coated with solid microparticles

Info

Publication number: WO2013039097A1
Application number: PCT/JP2012/073304
Authority: WO
Inventors: 一之岸; 秀雄三井
Original assignee: 株式会社ファシリティ
Priority date: 2011-09-14
Filing date: 2012-09-12
Publication date: 2013-03-21
Also published as: TW201321556A; JP5802275B2; JPWO2013039097A1; TWI551732B

Abstract

The purpose of this invention is to provide a durable, high-performance wire coated with solid microparticles, the wire allowing solid microparticles such as diamond particles to be affixed to the wire in a stable manner; and to provide a method for producing the wire coated with solid microparticles. In order to achieve this objective, there is provided a wire coated with solid microparticles or the like in which the solid microparticles are affixed to the outer peripheral surface of the wire, wherein the wire or the like coated with solid microparticles is characterized that the surface of the wire is provided with: a nickel electroplating layer containing solid microparticles, the microparticles being dispersed, surface-modified solid microparticles with an inorganic coating layer; and a nickel plating overcoat layer on the surface of the nickel electroplating layer containing solid microparticles.

Description

Solid particulate adhering wire and method for producing the solid particulate adhering wire

The present invention relates to a solid fine particle adhering wire in which solid fine particles such as diamond are fixed to the outer peripheral surface of the wire, and a method for producing the solid fine particle adhering 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. It is suitable for cutting highly difficult-to-process materials, and its demand is increasing. In recent years, there has been a demand for further improvement in the performance of a tool (wire saw) for cutting a highly brittle material provided with such a solid fine particle-attached wire and a longer life of the product.

As a method for producing such a solid fine particle-attached wire, a nickel or titanium coat layer is formed on the surface of the solid fine particle, and the solid fine particle having the nickel or titanium coat layer is added to a nickel plating solution. A composite plating method in which solid fine particles are deposited together with nickel on the surface of the wire is known. For example, Patent Document 1 and Patent Document 2 disclose a method of performing composite plating using a solid fine particle having a nickel coating layer added to a nickel plating solution and eutecting nickel and solid fine particles on the wire surface. Has been. In addition, prior to such composite plating, an attempt has been made to improve the amount of solid fine particles adhering to the wire surface by previously performing nickel plating as a base on the surface of the wire.

JP 2006-55952 A JP 2011-140095 A

However, in the composite plating using the solid fine particles having a nickel coating layer added to the nickel plating solution, the solid fine particles are difficult to disperse and precipitate on the wire surface, that is, a plurality of solid fine particles are likely to aggregate. There was a problem that analysis control was difficult. Further, when solid fine particles having a titanium coat layer are used, there is a problem that the plating layer formed on the wire surface is easily peeled off, the life of the plating solution is short, and the operation stability is lacking.

Accordingly, the present invention has been made to solve the conventional technical problem, and can solidly fix solid fine particles such as diamond on a wire, has high performance, and has long-term performance. An object of the present invention is to provide a usable solid fine particle-attached wire and a method for producing the solid fine particle-attached wire.

Therefore, as a result of intensive studies, the inventors of the present invention have achieved the above-mentioned problems by adopting the solid fine particle-attached wire and the method for producing the solid fine particle-attached wire described below.

Solid fine particle adhesion wire: The solid fine particle adhesion wire according to the present invention is a solid fine particle adhesion wire in which solid fine particles are fixed to the outer peripheral surface of the wire, and the surface of the wire is provided with an inorganic coating layer subjected to surface modification treatment. A solid fine particle-containing electrolytic nickel plating layer containing dispersed solid fine particles, and an overcoat nickel plating layer on the surface of the solid fine particle-containing electrolytic nickel plating layer.

It is preferable to use a solid fine particle-attached wire according to the present invention that has an inorganic protective layer on the surface of the wire.

In the solid fine particle adhesion wire according to the present invention, it is preferable that the particle surface is made a charged surface by surface modification treatment of the particle surface of the solid fine particle with an inorganic coat layer.

In the solid fine particle-attached wire according to the present invention, it is preferable that 10 to 60 solid fine particles with an inorganic coat layer having a particle size of 0.01 to 100 μm are attached within a length range of 500 μm of the wire.

The solid fine particle-attached wire according to the present invention preferably uses one or more selected from palladium-coated diamond particles, nickel-coated diamond particles, and titanium-coated diamond particles as the solid fine particles with an inorganic coat layer.

Production method of solid fine particle-attached wire: The production method of the solid fine particle-attached wire according to the present invention described above preferably employs a production method including the following steps a to d.

Step a. A step of preparing solid fine particles with an inorganic coat layer comprising an inorganic coat layer on the surface of the solid fine particles.
Step b. A step of subjecting the surface of the solid fine particles with an inorganic coat layer to surface modification treatment of the solid fine particles with an inorganic coat layer using a surface modifier in order to impart a predetermined polarity.
Step c. The solid fine particles with inorganic coat layer that have been subjected to the surface modification treatment are placed in a nickel plating solution to be suspended, and nickel is deposited on the wire surface by electrolytic plating, and at the same time, the solid fine particles with inorganic coat layer are attached. A step of applying composite plating to form a solid fine particle-containing nickel plating layer on the surface of the wire.
Step d. The process of overcoating nickel plating on the solid fine particle content nickel plating layer of the wire surface.

In the method for producing a solid fine particle-attached wire according to the present invention, it is preferable to use a wire having an inorganic protective layer on its surface.

In the method for producing a solid fine particle-attached wire according to the present application, the surface modifier in the step b preferably includes one or more of an amine-based, non-ionic, and cationic surfactant.

Moreover, in the method for producing a solid fine particle-attached wire according to the present application, it is also preferable that alcohol amines and a nonionic surfactant are included as the surface modifier in the step b.

In the method for producing a solid fine particle-attached wire according to the present application, it is preferable that the solid fine particles have a particle diameter of 0.01 to 100 μm.

In the method for producing a solid fine particle-attached wire according to the present application, the overcoat nickel plating layer formed in the step d preferably has a thickness in the range of 0.1 to 40 μm.

In the method for producing a solid fine particle-attached wire according to the present application, it is preferable to use a wire having a diameter of 0.02 mm to 3.0 mm.

The solid fine particle-attached wire according to the present application includes a solid fine particle-containing electrolytic nickel plating layer in which solid fine particles with an inorganic coat layer are dispersed and contained on the surface of the wire, and an overcoat nickel plating layer on the surface of the solid fine particle-containing electrolytic nickel plating layer And. The solid fine particle-attached wire is stably provided with 20 or more solid fine particles with an inorganic coat layer having a particle size of 0.01 to 100 μm within a length range of 500 μm of the wire. As a result, as a wire saw, it exhibits good cutting performance, and solid fine particles with an inorganic coat layer on the outer peripheral surface of the wire are less likely to fall off during the cutting work of the object to be cut, enabling long-term stable use. .

In addition, the solid fine particle-attached wire according to the present application is obtained by subjecting the particle surface to a surface modification treatment using a predetermined surface modifier in advance as a solid fine particle with an inorganic coat layer in the production process. By using it, the solid fine particles with the inorganic coat layer are appropriately dispersed and uniformly attached to the outer peripheral surface of the wire.

And, as a manufacturing method of the solid fine particle adhesion wire according to the present application, while using the plating method, it was added to the plating solution by using the solid fine particles with an inorganic coat layer that had been subjected to a predetermined surface modification treatment in advance. The amount of solid fine particles with inorganic coat layer attached to the wire can be increased in proportion to the amount of solid fine particles with inorganic coat layer, and the amount of solid fine particles with inorganic coat layer attached to the surface of the wire can be controlled. Became.

It is a mimetic diagram of the section of the solid particulate adhesion wire concerning this application. It is a photograph which shows the state of the wire surface which gave electrolytic nickel plating using the electroplating liquid of diamond content 5g / L of Example 1. FIG. It is a photograph which shows the state of the wire surface which gave electrolytic nickel plating using the electrolytic plating liquid of diamond content 10g / L of Example 2. FIG. It is a photograph which shows the state of the wire surface which gave electrolytic nickel plating using the electroplating liquid of diamond content 15g / L of Example 3. FIG. It is a photograph which shows the state of the wire surface which gave electrolytic nickel plating using the electroplating liquid of diamond content 10g / L of Example 4. FIG. It is a photograph which shows the state of the wire surface which gave electrolytic nickel plating using the electrolytic plating liquid of diamond content 10g / L of Example 5. FIG. It is a photograph which shows the state of the wire surface which gave electrolytic nickel plating using the electroplating liquid of diamond content 5g / L of the comparative example 1.

Hereinafter, preferred embodiments of the solid fine particle-attached wire and the method for producing the solid fine particle-attached wire according to the present invention will be described.

[Form of solid fine particle adhesion wire]
First, the form of the solid fine particle adhesion wire according to the present invention will be described. The solid fine particle adhesion wire according to the present invention is a wire with solid fine particles formed by fixing solid fine particles to the outer peripheral surface of the wire. That is, the solid fine particle-attached wire according to the present invention has a solid fine particle-containing electrolytic nickel plating layer dispersedly containing “solid fine particles with an inorganic coating layer” on the surface of the wire, and the surface of the solid fine particle-containing electrolytic nickel plating layer. A coat nickel plating layer is provided. The following is a breakdown of each necessary element and term.

<Electrolytic nickel plating layer containing solid fine particles>
This solid fine particle-containing electrolytic nickel plating layer directly contacts and covers the surface of the wire, and solid fine particles with an inorganic coating layer are dispersed and contained in the electrolytic nickel plating layer. 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 limited to a mere surface coating, but has a good wettability with a wire described later and exhibits chemical affinity. Therefore, the electrolytic nickel layer provided on the wire surface by an electrolytic method has good adhesion. As the nickel plating solution used for the configuration of the solid fine particle-containing electrolytic nickel plating layer, a pure nickel plating solution or a nickel alloy (nickel-phosphorous, nickel-cobalt, nickel-zinc or other nickel-based alloy) plating solution should be used. Is possible.

Wire: The wire used in the present application is not particularly limited as long as the surface can be electroplated and has a certain strength, and can be appropriately selected according to the intended use. 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, when the wire diameter is less than 0.02 mm, the solid with an inorganic coat layer with respect to the wire surface in the manufacturing method using the solid fine particles with an inorganic coat layer having a predetermined particle diameter described later This is not preferable because it tends to make it difficult to attach fine particles efficiently. On the other hand, since the upper limit of the diameter of this wire changes with uses, it is defined as a temporary standard. For example, in the case of a solid fine particle attached wire used for cutting a silicon wafer, 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. When 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. And in the case of the solid fine particle adhesion wire which is going to cut structures, such as reinforced concrete and structural steel, 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.

And it is preferable to use the solid fine particle adhering wire according to the present invention provided with an inorganic protective layer on the surface of the wire. 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. In addition, depending on the type of the inorganic protective layer, it becomes possible to stabilize the adhesion state of solid fine particles described later. As the inorganic protective layer, nickel, nickel alloy (Ni—Co, Ni—Sn, Ni—Zn), Cu, copper alloy (Cu—Zn, Cu—Sn), or the like can be used.

Solid fine particles: The solid fine particles used as the core material of the solid fine particles with the inorganic coat layer used in the present application will be described. The solid fine particles mentioned here can be appropriately selected according to the use of the solid fine particle-attached wire. For example, cerium oxide, silicon oxide (quartz, fused silica, etc.), alumina, silicon carbide, silicon nitride, zirconium oxide, diamond, etc. Fine particles. In particular, when the solid fine particle-attached wire is used 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 to 100 μm are preferably used. When the particle size of the solid fine particles is less than 0.01 μm, the surface of the solid fine particle adhering wire becomes too smooth, and the significance of adhering the solid fine particles to the wire is not limited to wire saw use but also in other uses. It is not preferable because it will be sunk. On the other hand, when the particle size of the solid fine particles exceeds 100 μm, even if a wire of 0.8 mm, which is the maximum diameter of the wire used by the invention according to the present application, is used, a uniform dispersibility is maintained on the wire surface. There is a tendency for solid particulates to be difficult to attach, and there is no such market requirement. In particular, for the wire having a diameter of 0.08 to 0.2 mm when the solid fine particle adhering wire is used for the purpose of cutting a silicon wafer for solar cells, the solid fine particle having a particle size of 4 to 40 μm is used. This is more preferable because it 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, and the life of the wire saw can be extended.

Solid fine particles with inorganic coat layer: The solid fine particles with inorganic coat layer referred to here are those having an inorganic coat layer composed of a metal component on the surface of the solid fine particles. And the component of this inorganic coat layer can be appropriately selected and used according to the application of the solid fine particle-attached wire. More specifically, the inorganic fine particles with an inorganic coat layer mentioned here are assumed to be solid fine particles with a palladium coat layer, solid fine particles with a nickel coat layer, solid fine particles with a titanium coat layer, and the like. 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 by a plating method, and good adhesion is obtained.

These solid fine particles with an inorganic coating layer are uniformly dispersed in the solid fine particle-containing electrolytic nickel plating layer. The solid fine particles with an inorganic coat layer are preferably subjected to a surface modification treatment with a surface modifier in advance, and the surface of the solid fine particles with an inorganic coat layer is used as a charged surface to give a predetermined polarity to the particle surface. In this case, the solid particles with a palladium coat layer can selectively use any charged state of nonionic particles and cationic particles according to the polarization state of the wire. That is, to give a specific example, when the wire is polarized to the cathode during electrolytic nickel plating, the surface of the solid fine particles with inorganic coating layer is charged to the opposite positive electrode with respect to the plating solution. become. By such surface modification treatment of the solid fine particles with an inorganic coat layer, the solid fine particles are uniformly dispersed and adhered to the wire surface during the electrolytic plating in the manufacturing method of the following solid fine particle-attached wire, The amount of the solid fine particles with the inorganic coat layer attached to the solid fine particle attachment wire can be obtained in proportion to the amount of the solid fine particles with the inorganic coat layer. This surface modification treatment will be further described in a later manufacturing method.

<Overcoat nickel plating layer>
The overcoat nickel plating layer is provided on the surface of the solid fine particle-containing electrolytic nickel plating layer containing the 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” referred to here is preferably composed of a pure nickel plating solution and a nickel alloy (nickel-based alloy such as nickel-phosphorus, nickel-cobalt, nickel-zinc) 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.

By adopting a solid fine particle-containing electrolytic nickel plating layer in which the solid fine particles with a palladium coat layer are dispersed and contained on the wire surface described above, and a solid fine particle adhesion wire having an overcoat nickel plating layer on the surface thereof, It is possible to effectively prevent the attached solid fine particles from falling off. Thereby, it is possible to realize a solid particulate adhering wire that is highly reliable and can be used for a long time.

[Manufacturing form of wire with solid fine particles]
Next, the manufacturing method of the solid fine particle adhesion wire which concerns on this invention is demonstrated.

Wire cleaning treatment: It is preferable to first degrease the surface of the wire used in the production of the solid fine particle-attached wire according to the present invention and clean it. 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 method for producing a solid fine particle-attached wire according to the present invention includes the following steps a to d.

Step a. : In this step, solid particles with an inorganic coat layer having an inorganic coat layer on the surface of the solid particles are prepared. Therefore, a solid fine particle core material with an inorganic coat layer (the fine particles such as cerium oxide, silicon oxide (quartz, fused silica, etc.), alumina, silicon carbide, zirconium oxide, diamond, Teflon (registered trademark), etc.) As the particles provided with an inorganic coat layer composed of a metal component on the particle surface, solid fine particles with a palladium coat layer, solid fine particles with a nickel coat layer, solid fine particles with a titanium coat layer, and the like are prepared. Commercial products corresponding to these solid fine particles with an inorganic coat layer may be used.

However, among the solid fine particles with the inorganic coat layer, the solid fine particles with the palladium coat layer are preferably coated 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. As 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 to 20 mg per 1 g of solid fine particles. When 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 wettability with the nickel or nickel alloy precipitation component formed by plating is sufficiently improved. This is not preferable because good adhesion cannot be obtained. On the other hand, even if 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. Since the amount of palladium adsorbed exceeds 10 mg per gram of solid fine particles, the eutectoid effect of nickel and solid fine particles is improved only moderately. Therefore, a more preferable amount of palladium adsorbed is 0.1 per gram of solid fine particles. ~ 10 mg.

Next, 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. At this stage, 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.

In both the first palladium coating method and the second palladium coating method described above, 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 in the invention according to the present application, it is sufficient that the surface of the solid fine particles can be covered with the palladium coat layer. Note that the method is not to be construed as limited.

Step b. This step is a surface modification treatment step in which the surface of the solid fine particles with an inorganic coat layer is brought into contact with a surface modifier in the step a to charge it to a predetermined polarity. This process is a process that is not present in the production of a conventional solid fine particle-attached wire. In the conventional method for producing a solid fine particle-attached wire, it has been difficult to effectively attach the solid fine particles to the wire. Therefore, as a result of intensive studies by the present inventors, after providing an inorganic coat layer on the surface of solid fine particles, surface modification treatment with a surface modifying agent is performed in advance to stabilize the polarity of the surface. I thought of that. As a result, it was found that the amount of solid fine particles attached to the wire surface can be arbitrarily controlled in the step of forming the solid fine particle-containing electrolytic nickel plating layer, the amount of attachment can be significantly increased, and evenly dispersed. is there.

Specifically, when the wire is polarized to the cathode in the plating solution in the step c (solid fine particle-containing electrolytic nickel plating layer forming step) described later, the surface of the solid fine particles with the inorganic coating layer is charged to the positive electrode in advance. Apply the process to be. By so doing, it was conceived that solid fine particles easily adhere to the surface of the later wire. This is because the surface of the solid fine particles is charged to the positive electrode against the wire polarized to the cathode during electrolytic plating, and the solid fine particles themselves are stabilized in a positively charged state. This is because solid fine particles are easily attracted to the wire during plating.

The surface modification treatment at this time can be carried out by selecting an optimum method from a method of immersing solid fine particles in a surface treatment agent, a method of spraying the surface treatment agent on the surface of the solid fine particles, and the like. 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.

When forming the solid nickel-containing electrolytic nickel plating layer, solid fine particles with an inorganic coating layer are attached to the wire surface, and at the same time, nickel components are precipitated from nickel ions having a positive charge. Therefore, in this surface modification treatment, it is necessary to use a surface modifier that can be stabilized by imparting a positive polarity to the surface of the solid fine particles with the inorganic coat layer. As such a surface modifier, it is preferable to use one containing an amine surfactant, a nonionic surfactant or a cationic surfactant, and in particular, a nonion containing an alcohol amine. It is preferable to use a system surfactant. In such a surface modifier, 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.

Step c. : This step is a step of forming a solid fine particle-containing electrolytic nickel plating layer in which composite plating is performed to form an electrolytic nickel plating layer containing inorganic coated solid fine particles on the surface of the wire by an electrolytic plating method. The solid nickel-containing electrolytic nickel plating method applied here will be described below.

First, wire will be described. The wire used here is preferably one having an inorganic protective layer on its surface. As described above, nickel, nickel alloy (Ni—Co, Ni—Sn, Ni—Zn), Cu, copper alloy (Cu—Zn, Cu—Sn), etc. can be used as the metal component constituting the inorganic protective layer. However, in consideration of the corrosion resistance performance and the adhesion stability of the solid fine particles, the use of nickel or a nickel alloy is optimal. 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 0.1 μm or less. As a current supply method at this time, it is naturally 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” that repeats an energized state and a current stopped state is used. It is also preferable to employ the “plating method”. 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 adopt 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 .

The following is a list of typical bath compositions used for strike plating. As an example, in the case of nickel strike plating, it is possible to use a sulfamic acid-based nickel plating bath and a watt bath described later. In the case of copper cyanide strike plating, an electrolytic solution containing 20 to 35 g / L of copper cyanide, 37 to 60 g / L of sodium cyanide, 3 to 5 g / L of potassium hydroxide, and 10 to 20 g / L of Rochelle salt. A liquid can be used. In the case of copper pyrophosphate strike plating, 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.

Next, as the plating solution for forming the solid fine particle-containing electrolytic nickel plating layer, the solid fine particles with the inorganic coating layer subjected to the surface modification treatment in the step b are suspended in the plating solution containing the nickel component. Use the same thing. As the plating solution, a commercially available electrolytic nickel plating solution obtained by suspending solid fine particles with an inorganic coating layer surface-modified in step b can be used, or a Watt bath or a sulfamic acid bath applied to nickel plating. Or the like, in which solid fine particles with an inorganic coat layer subjected to surface modification treatment in step b are suspended may be used. For example, there is no particular limitation on the nickel plating solution at this time, and it is possible to adopt a bath composition and electrolytic conditions that allow smooth nickel plating. As an example, several nickel plating baths and plating conditions are listed below.

If a sulfamic acid nickel plating bath is used, nickel sulfamate tetrahydrate is 200 to 800 g / L, nickel chloride hexahydrate is 1 to 10 g / L, boric acid is 20 to 50 g / L, For example, a nickel plating composition having a pH of 3 to 5 is employed.

If a Watt-type nickel plating bath is used, nickel sulfate heptahydrate is 200 to 500 g / L, nickel chloride heptahydrate is 10 to 100 g / L, boric acid is 20 to 50 g / L, For example, a nickel plating composition having a pH of 3 to 5 is employed.

The content of solid fine particles with an inorganic coat layer in the plating solution for forming the solid nickel-containing electrolytic nickel plating layer is arbitrarily determined 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 to adopt an addition amount. For example, when obtaining a solid fine particle-attached wire for use in a wire saw, the solid fine particle content is preferably about 4 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 4 g / l, the wire saw does not have good cutting performance. On the other hand, if 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.

Then, by using a plating solution in which the above-described solid fine particles are suspended and applying general plating conditions, nickel and solid fine particles can be co-deposited on the surface of the wire. At this time, it is preferable to co-deposit so that 10 to 60, more preferably 20 to 50 solid fine particles adhere to the length of 500 μm of the wire. When the number of the solid fine particles is less than 10, it is not preferable because cutting performance as a wire saw is deteriorated. On the other hand, if the number of solid fine particles exceeds 60, the solid fine particles easily fall off during handling of the wire saw, and the cut surface of the workpiece tends to become rough, which is not preferable. Thereby, the solid nickel containing electrolytic nickel plating layer which contains the solid fine particle with a palladium coat layer in the form disperse | distributed on the surface of a wire can be formed.

Step d. This step is an overcoat nickel plating layer forming step of further performing nickel plating on the surface of the solid fine particle-containing electrolytic nickel plating layer obtained in the step c. The nickel plating method applied here is preferably an electrolytic plating method from the viewpoint of production speed. As the plating solution used in this step d, a commercially available nickel plating bath may be used, or a watt bath, a sulfamic acid bath or the like prepared by itself as described in detail in the above step c may be used. Absent.

Then, 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 to 60 ° C., and the wire is polarized to the cathode to Then, an overcoat nickel plating layer having a desired thickness is formed. Here, when 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. On the other hand, when the temperature of the nickel plating solution exceeds 60 ° C., it becomes difficult to use the vinyl chloride pipe, so that the restrictions on the constituent materials of the manufacturing equipment increase, and the water evaporation rate of the plating solution increases and the plating solution increases. This is not preferable because the variation in the composition of the material becomes large and stable plating operation becomes difficult. Other plating conditions are not particularly limited as long as smooth nickel plating is possible.

The overcoat nickel plating layer formed in this step d 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 to 40 μm. When the thickness of the overcoat nickel plating layer is less than 0.1 μm, 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. On the other hand, if the thickness of the overcoat nickel plating exceeds 40 μm 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, it is difficult to expose the top of the diamond immediately after the start of use as a wire saw when the plating thickness of the top of the diamond particle is increased. Since the initial cutting performance is deteriorated, it is not preferable.

Further, it is more preferable that the thickness of the overcoat nickel plating layer is 2 to 4 μm. The overcoat nickel plating layer preferably has a thickness of 0.1 to 40 μm. When the thickness of the overcoat nickel plating layer is 2 μm, 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. And even if the thickness of the overcoat nickel plating layer exceeds 4 μm, 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.

Here, a method for measuring the thickness of the overcoat nickel plating layer will be described. When the cross section of the solid fine particle adhering wire 1 is directly observed with a metal microscope, as schematically shown in FIG. 1, the wire 2, the inorganic protective layer (strike plating layer) 3, the solid fine particle 4, the overcoat nickel plating layer 5 However, it can be observed clearly. At this time, the thickness of the overcoat nickel plating layer 5 is measured at a location where the solid fine particles 4 do not exist in the overcoat nickel plating layer 5.

Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is limited to a following example and is not interpreted.

Wire: In the examples, a steel wire wire having a diameter of 0.12 mm was used. 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 provide an inorganic protective layer having a thickness of about 0.08 μm. The nickel strike plating at this time uses an electrolytic solution containing 240 g / L of nickel chloride and 125 g / L of hydrochloric acid, a pulse waveform is a rectangular wave, a frequency of 1000 Hz, a duty ratio (on: 20, off: 80), and a current density. It adopted the pulse electrolysis conditions of the ^{6A / dm 2 ~ 10A / dm} 2. Similar wires are used in other examples and comparative examples.

Solid fine particles: In the examples, diamond particles having an average particle diameter of 15 μm were used as the solid fine particles. And using this diamond particle, the solid fine particle adhesion wire was manufactured with the following method. Similar diamond particles are used in Example 2, Example 3 and Comparative Example described later.

Step a: In Example 1, a method of precipitating palladium and tin on the surface of diamond particles using a solution containing diamond particles as a main component of a palladium / tin colloid catalyst was adopted. In this example, a solution having a palladium concentration of 0.1 g / l, a tin concentration of 2 g / l, and 40 ° C. was used. After the diamond particles were immersed in this solution for 10 minutes, the diamond particles were taken out of the solution and washed with water. Thereafter, the diamond particles were immersed in sulfuric acid having a concentration of 50 g / l for 10 minutes. As a result, a palladium-coated layer was formed on the surface of the diamond particles to obtain “palladium-coated diamond particles”.

Step b: In this step, a surface modification treatment was performed on the particle surface of the “palladium-coated diamond particles” using a solution containing a nonionic surfactant containing an alcoholamine as a surface modifier. In this case, the surface modifier is a solution of 2-aminoethanol (primary amine) 1.0 to 30% by mass, nonionic surfactant 0.1 to 5.0% by mass, pH 9.0 to 12.5. Was used. In the surface modification treatment, “palladium-coated diamond particles” were placed in the surface modifier maintained at a liquid temperature of about 30 ° C. and immersed for 10 minutes, and then washed with water.

Step c: In this step, the surface-modified palladium-coated diamond particles after step b are put into an electrolytic nickel plating solution, and the “diamond particle-containing electrolytic nickel” in a suspended state with a palladium-coated diamond particle concentration of 5 g / L. A plating solution "was obtained. The diamond particle-containing electrolytic nickel plating solution uses a nickel sulfamate plating bath of 400 g / L nickel sulfamate tetrahydrate, 2 g / L nickel chloride hexahydrate, 35 g / L boric acid, pH 4.0. It was.

Then, the temperature of the diamond particle-containing electrolytic nickel plating solution is set to 50 ° C., electrolysis is performed at a current density of 15 A / dm ² , composite plating is performed on the surface of the degreased wire, and the palladium-coated diamond particles are dispersed. The contained “diamond particle-containing electrolytic nickel plating layer” was formed.

Step d: In this step, as a plating solution, nickel sulfamate tetrahydrate 450 g / L, nickel chloride hexahydrate 3 g / L, boric acid 40 g / L, pH 4.0 nickel sulfamate A plating bath was adopted. Then, on the surface of the diamond particle-containing electrolytic nickel plating layer provided on the wire surface in step c under the conditions that the temperature of the nickel plating solution is 50 ° C. and the current density is 15 A / dm ² , an “overcoat having a thickness of about 4 μm is formed. A “nickel plating layer” was formed, and a “diamond fine particle-attached wire” was manufactured.

The diamond fine particle-attached wire produced in Example 1 had about 24 palladium-coated diamond particles attached to the length of 500 μm of the wire as shown in FIG. The converted thickness of the “overcoat nickel plating layer” was 4.1 μm.

In Example 2, only the content of the palladium-coated diamond particles in step c was different from that in Example 1, and the other conditions were the same as in Example 1 to produce a diamond fine particle-attached wire. Below, only the conditions of the process c different from Example 1 are demonstrated.

In Example 2, an electrolytic plating solution was prepared by setting the concentration of palladium-coated diamond particles suspended in the sulfamic acid bath in step c to 10 g / L. The other conditions such as the temperature of the plating solution and the current density were the same as in Example 1.

As shown in FIG. 3, the diamond fine particle-attached wire produced in Example 2 had about 31 palladium-coated diamond particles attached to the length of 500 μm of the wire. The converted thickness of the “overcoat nickel plating layer” was 4.2 μm.

In Example 3, only the diamond particle content in step c was different from that in Example 1, and all other conditions were the same as in Example 1 to produce a diamond particle-attached wire. Below, only the conditions of the process c different from Example 1 are demonstrated.

In Example 3, an electrolytic plating solution was prepared by setting the concentration of the palladium-coated diamond particles suspended in the sulfamic acid bath in step c to 15 g / L. The other conditions such as the temperature of the plating solution and the current density were the same as in Example 1.

In the diamond fine particle-attached wire manufactured in Example 3, about 46 palladium-coated diamond particles were attached to the length of 500 μm of the wire as shown in FIG. Further, the converted thickness of the “overcoat nickel plating layer” was 4.3 μm.

In this Example 4, instead of the palladium-coated diamond particles prepared in Step a of Example 1, commercially available nickel-coated diamond particles having the same particle diameter were used.

And the content similar to the content of diamond particles in step c of Example 2 is adopted. That is, in step c of Example 4, “step b is completed and the surface-modified nickel-coated diamond particles are placed in an electrolytic nickel plating solution, and the solid particles containing suspended solid particles having a diamond particle concentration of 10 g / L are contained. An electrolytic nickel plating solution was obtained "except that the point was different from that of Example 1, and all other conditions were the same as in Example 1 to produce a nickel-coated diamond particle-attached wire.

As shown in FIG. 5, the diamond fine particle-attached wire manufactured in Example 4 had about 30 nickel-coated diamond particles attached to the length of 500 μm of the wire. The converted thickness of the “overcoat nickel plating layer” was 4.1 μm.

In this Example 4, instead of the palladium-coated diamond particles prepared in Step a of Example 1, commercially available titanium-coated diamond particles having the same particle diameter were used.

And the content similar to the content of diamond particles in step c of Example 2 is adopted. That is, in Step c of Example 4, “Step b is completed and the surface-modified titanium-coated diamond particles are put in an electrolytic nickel plating solution, and the solid particles containing suspended solid particles having a diamond particle concentration of 10 g / L are contained. An electrolytic nickel plating solution was obtained ”except that the point was different from Example 1, and the other conditions were the same as in Example 1 to produce a titanium-coated diamond particle-attached wire.

In the diamond fine particle-attached wire manufactured in Example 4, about 32 titanium-coated diamond particles were attached to the length of 500 μm of the wire as shown in FIG. The converted thickness of the “overcoat nickel plating layer” was 4.2 μm.

Comparative example

[Comparative Example 1]
In Comparative Example 1, the palladium-coated diamond particles obtained in Step a of Example 1 were subjected to the plating in Step c without performing the surface modification treatment in Step b to produce a solid fine particle-attached wire. Thereby, the adhesion amount of diamond particles to the wire when the surface modification treatment in the step b was not performed was verified.

In Comparative Example 1, the surface-modifying treatment step of the surface modifier in Step b of Example 1 was not performed, and the diamond particles coated with palladium obtained in Step a of Example 1 were replaced with Step c of Example 1. A plating solution was prepared by suspending in the sulfamic acid bath described in 1) at a concentration of 5 g / L. Note that Comparative Example 1 is different from Example 1 only in that step b is not performed, and other steps, diamond particles to be used, wires, plating conditions, etc. are all the same as those in the above-described example. did.

The diamond fine particle-attached wire produced in Comparative Example 1 had about 8 palladium-coated diamond particles attached to the 500 μm length of the wire as shown in FIG. The converted thickness of the “overcoat nickel plating layer” was 4.1 μm.

[Comparative Example 2]
In Comparative Example 2, the palladium-coated diamond particles obtained in Step a of Example 1 were subjected to the plating in Step c without performing the surface modification treatment in Step b to produce a solid fine particle-attached wire. Thereby, the adhesion amount of diamond particles to the wire when the surface modification treatment in the step b was not performed was verified.

In Comparative Example 1, the surface-modifying treatment step of the surface modifier in Step b of Example 1 was not performed, and the diamond particles coated with palladium obtained in Step a of Example 1 were replaced with Step c of Example 1. A plating solution was prepared by suspending in the sulfamic acid bath described in 1) at a concentration of 10 g / L. Note that Comparative Example 1 is different from Example 1 only in that step b is not performed, and other steps, diamond particles to be used, wires, plating conditions, etc. are all the same as those in the above-described example. did.

The diamond fine particle-attached wire manufactured in Comparative Example 2 had the same form as in FIG. 7 and had about 8 palladium-coated diamond particles attached to the length of 500 μm of the wire. The converted thickness of the “overcoat nickel plating layer” was 4.0 μm.

[Comparative Example 3]
In Comparative Example 3, the palladium-coated diamond particles obtained in Step a of Example 1 were subjected to the plating in Step c without performing the surface modification treatment in Step b to produce a solid fine particle-attached wire. Thereby, the adhesion amount of diamond particles to the wire when the surface modification treatment in the step b was not performed was verified.

In Comparative Example 1, the surface-modifying treatment step of the surface modifier in Step b of Example 1 was not performed, and the diamond particles coated with palladium obtained in Step a of Example 1 were replaced with Step c of Example 1. A plating solution was prepared by suspending in the sulfamic acid bath described in 1) at a concentration of 15 g / L. Note that Comparative Example 1 is different from Example 1 only in that step b is not performed, and other steps, diamond particles to be used, wires, plating conditions, etc. are all the same as those in the above-described example. did.

The diamond fine particle-attached wire manufactured in Comparative Example 2 had the same form as that shown in FIG. 7, and about 9 palladium-coated diamond particles were attached to the 500 μm length of the wire. The converted thickness of the “overcoat nickel plating layer” was 4.1 μm.

[Consideration from comparison between Example and Comparative Example]
The following Table 1 shows the observation results of the manufactured diamond fine particle-attached wires so that the comparison between Examples and Comparative Examples is easy.

The effect of the presence or absence of surface modification treatment will be described with reference to Table 1. First, what can be understood from the embodiment will be described. In Examples 1 to 3, the content of diamond particles contained in the electrolytic nickel plating solution in step c was changed. As can be seen from Examples 1 to 3, when the content of diamond particles contained in the electrolytic nickel plating solution is changed from 5 g / l → 10 g / l → 15 g / l, it adheres to the diamond fine particle adhering wire. As the number of diamond particles increases from 24 to 31 to 46, the number of diamond particles adhering to the diamond fine particle attachment wire increases proportionally with the increase in the amount of diamond particles contained in the electrolytic nickel plating solution. I understand that

Here, looking at Comparative Examples 1 to 3, these Comparative Examples also changed the content of diamond particles contained in the electrolytic nickel plating solution from 5 g / l → 10 g / l → 15 g / l. However, it can be understood that the number of diamond particles adhering to the diamond fine particle adhering wire is 8 to 9, and the change in the adhering amount of diamond particles is small. In other words, in the case of the comparative example, it can be seen that even when the content of diamond particles contained in the electrolytic nickel plating solution is increased, the number of diamond particles attached to the diamond fine particle attachment wire does not increase in proportion. Moreover, in the case where the content of diamond particles contained in the electrolytic nickel plating solution is the same, it is easy to see that the number of adhered particles in the example is larger as compared with the example and the comparative example. Understandable.

From the above, in the production of the diamond fine particle-attached wire, a surface modification treatment is performed on the surface of the palladium-coated diamond particles using a solution containing a nonionic surfactant containing an alcoholamine as a surface modifier. Thus, it can be understood that the diamond particles can be uniformly and reliably attached to the surface of the diamond fine particle-attached wire, and the amount of the diamond particles to be attached can be controlled.

When the solid fine particle-attached wire according to the example described above and the solid fine particle-attached wire according to the comparative example are used as a wire saw, the solid fine particle according to the example is compared with the solid fine particle-attached wire according to the comparative example. It can be seen that the cutting performance of the attached wire is remarkably high and can be used for a long time.

As described above, the solid fine particle adhesion wire obtained by adopting the manufacturing method according to the present invention significantly improves the adhesion amount of the solid fine particles adhering to the wire, and effectively suppresses the falling off of the adhering solid fine particles. It is what. Thereby, it becomes possible to provide the solid fine particle adhesion wire which is excellent in the cutting performance as a wire saw, and can be used for a long term at low cost. Such solid fine particle adhering wire can be used suitably in the manufacturing process of solar cells, silicon wafers for semiconductors, etc., because it can cut high brittle materials such as single crystal silicon ingots with high precision. It is. Further, 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.

1 Solid fine particle adhesion wire 2 Wire 3 Inorganic protective layer (Strike plating layer)
4 Solid fine particles 5 Overcoat nickel plating layer

Claims

In the solid fine particle adhesion wire formed by fixing solid fine particles to the outer peripheral surface of the wire,
On the surface of the wire, a solid fine particle-containing electrolytic nickel plating layer containing dispersed inorganic fine particles with an inorganic coat layer subjected to a surface modification treatment,
A solid fine particle adhesion wire comprising an overcoat nickel plating layer on a surface of the solid fine particle-containing electrolytic nickel plating layer.
The solid fine particle-attached wire according to claim 1, wherein the wire includes an inorganic protective layer on a surface thereof.
3. The solid fine particle-attached wire according to claim 1, wherein the surface modification treatment uses a surface modifying agent capable of making the particle surface of the solid fine particles with an inorganic coat layer a charged surface. 4.
The solid according to any one of claims 1 to 3, wherein 10 to 60 solid fine particles with an inorganic coat layer having a particle size of 0.01 to 100 µm are attached in a length range of 500 µm of the wire. Fine particle adhesion wire.
The solid fine particle adhesion according to any one of claims 1 to 4, wherein the solid fine particles with an inorganic coat layer are one or more selected from palladium-coated diamond particles, nickel-coated diamond particles, and titanium-coated diamond particles. wire.
A method for producing a solid fine particle-attached wire according to any one of claims 1 to 5,
A method for producing a solid fine particle-attached wire, comprising the following steps a to d.
Step a. A step of preparing solid fine particles with an inorganic coat layer comprising an inorganic coat layer on the surface of the solid fine particles.
Step b. A step of subjecting the surface of the solid fine particles with an inorganic coat layer to surface modification treatment of the solid fine particles with an inorganic coat layer using a surface modifier in order to impart a predetermined polarity.
Step c. The solid fine particles with inorganic coat layer that have been subjected to the surface modification treatment are placed in a nickel plating solution to be suspended, and nickel is deposited on the wire surface by electrolytic plating, and at the same time, the solid fine particles with inorganic coat layer are attached. A step of applying composite plating to form a solid fine particle-containing nickel plating layer on the surface of the wire.
Step d. The process of overcoating nickel plating on the solid fine particle content nickel plating layer of the wire surface.
The said wire is a manufacturing method of the solid fine particle adhesion wire of Claim 6 using what equips the surface with an inorganic protective layer.
The method for producing a solid fine particle-attached wire according to claim 6 or 7, wherein the surface modifier in the step b includes one or more of any one of an amine-based, non-ionic, and cationic surfactant.
The method for producing a solid fine particle-attached wire according to any one of claims 6 to 8, wherein the surface modifier in the step b includes alcohol amines and a nonionic surfactant.
10. The method for producing a solid fine particle-attached wire according to claim 6, wherein the solid fine particles have a particle diameter of 0.01 to 100 μm.
11. The method for producing a solid fine particle-attached wire according to claim 6, wherein the overcoat nickel plating layer formed in the step d has a thickness of 0.1 to 40 μm.
12. The method for producing a solid fine particle-attached wire according to claim 6, wherein the wire has a diameter of 0.02 mm to 3.0 mm.