TW201321556A - Wire coated with solid microparticles, and method for producing wire coated with solid microparticles - Google Patents
Wire coated with solid microparticles, and method for producing wire coated with solid microparticles Download PDFInfo
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- TW201321556A TW201321556A TW101133436A TW101133436A TW201321556A TW 201321556 A TW201321556 A TW 201321556A TW 101133436 A TW101133436 A TW 101133436A TW 101133436 A TW101133436 A TW 101133436A TW 201321556 A TW201321556 A TW 201321556A
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Classifications
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- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D99/00—Subject matter not provided for in other groups of this subclass
Abstract
Description
本案發明，係關於在線的外周面固著鑽石等的固體微粒子的固體微粒子附著的線及該固體微粒子附著的線之製造方法。 The invention of the present invention relates to a method of attaching a solid fine particle of a solid fine particle such as a diamond to an outer peripheral surface of a wire, and a method of manufacturing a wire to which the solid fine particle adheres.
在線的外周面固著鑽石等的固體微粒子而成的固體微粒子附著的線，係適合用於太陽能電池用的矽晶圓、半導體用的矽晶圓、LED用途之藍寶石、如陶瓷或石材等硬質而脆性特性高的難加工材料的切斷，而其需求變高。近幾年，具備如此之固體微粒子附著的線的高脆弱性材料切斷用的工具(線鋸)被要求進一步的性能提升與產品的長壽化。 A line of solid fine particles in which solid particles such as diamonds are adhered to the outer peripheral surface of the wire is suitable for use in tantalum wafers for solar cells, tantalum wafers for semiconductors, sapphire for LED applications, and hard materials such as ceramics or stone. The cutting of difficult-to-machine materials with high brittle characteristics is required, and the demand thereof becomes high. In recent years, tools for cutting highly fragile materials (wire saws) having such a line to which solid particles adhere have been required to further improve performance and longevity of products.
作為該固體微粒子附著的線之製造方法，已知有於固體微粒子的表面上形成鎳或鈦的塗層，使用具有該鎳或鈦的塗層的固體微粒子添加於鎳鍍液者作為鍍液，使固體微粒子與鎳一起析出在線的表面上的複合鍍法。例如，於專利文獻1(日本國專利申請：特開2006-55952號公報)及專利文獻2(日本國專利申請：特開2011-140095號公報)，揭示有將具有鎳塗層的固體微粒子添加於鎳鍍液者進行複合鍍，使鎳與固體微粒子共析於線表面的方法。此外，亦有於如此之複合鍍之前，預先對線的表面進行成為底層之鍍鎳，提升固體微粒子對線表面的附著量之嘗試。 As a method for producing the wire to which the solid fine particles adhere, a coating layer in which nickel or titanium is formed on the surface of the solid fine particles is known, and a solid fine particle having a coating layer of the nickel or titanium is added to the nickel plating solution as a plating solution. A composite plating method in which solid fine particles are deposited on the surface of the wire together with nickel. For example, the addition of solid fine particles having a nickel coating is disclosed in the patent document 1 (Japanese Patent Application Laid-Open No. Hei. No. 2006-55952) and the patent document 2 (Japanese Patent Application No. 2011-140095). A method in which a nickel plating solution is subjected to composite plating to coexitate nickel and solid fine particles on a wire surface. In addition, prior to such composite plating, the surface of the wire was previously subjected to nickel plating as a primer layer, and an attempt was made to increase the amount of solid particles attached to the surface of the wire.
但是，以使用具有鎳塗層之固體微粒子添加於鎳鍍液之複合鍍，難以使固體微粒子分散析出於線的表面，即，有許多的固體微粒子容易團聚，而難以控制共析之問題。此外，使用具有鈦塗層的固體微粒子時，形成於線表面的鍍層容易剝落，並且，鍍液的壽命短，有缺乏操作穩定性的問題。 However, it is difficult to disperse and deposit the solid fine particles on the surface of the wire by using the composite plating having the nickel-coated solid fine particles added to the nickel plating solution, that is, many solid fine particles are easily agglomerated, and it is difficult to control the problem of eutectoid. Further, when solid fine particles having a titanium coating layer are used, the plating layer formed on the surface of the wire is easily peeled off, and the life of the plating solution is short, which has a problem of lack of operational stability.
因此，本案發明，係為解決該先前技術上的課題而完成者，以提供可將鑽石等的固體微粒子穩定地固定於線，高性能且可長期使用之固體微粒子附著的線及該固體微粒子附著的線之製造方法為目標。 Therefore, the present invention has been made to solve the problems of the prior art, and to provide a wire capable of stably fixing solid fine particles such as diamonds to a wire, and a solid particle capable of long-term use and adhesion of the solid microparticles. The manufacturing method of the line is the goal.
因此，本案發明者們進行專心研究的結果，藉由採用以下所述的固體微粒子附著的線及該固體微粒子附著的線之製造方法達成上述課題。 Therefore, as a result of intensive research by the inventors of the present invention, the above problems have been attained by using a method in which a solid fine particle adhered to the following and a method of manufacturing the solid fine particle adhered to the wire.
固體微粒子附著的線：關於本案發明之固體微粒子附著的線，其係在線的外周面固著固體微粒子而成的固體微粒子附著的線，其特徵在於：於該線的表面，分散含有施以表面改質處理的附有無機塗層之固體微粒子之含有固體微粒子之電鍍鎳層，及於該含有固體微粒子之電鍍鎳層的表面具備保護鍍鎳層。 The line to which the solid fine particles adhere is a line to which the solid fine particles adhered to the present invention is a line to which solid fine particles are adhered to the outer peripheral surface of the wire, and is characterized in that the surface of the line is dispersed and contains a surface to be applied. The electroplated nickel layer containing the solid fine particles with the inorganic coated solid fine particles and the surface of the electroplated nickel layer containing the solid fine particles are provided with a protective nickel plating layer.
關於本案發明之固體微粒子附著的線，使用於上述線的表面具備無機保護層者為佳。 The line to which the solid fine particles adhered in the invention of the present invention is preferably used in the case where the surface of the above-mentioned wire is provided with an inorganic protective layer.
關於本案發明之固體微粒子附著的線，藉由上述附有無機塗層之固體微粒子之粒子表面之表面改質處理，使該粒子表面為帶電表面為佳。 Regarding the line to which the solid fine particles adhered in the invention of the present invention, the surface of the particles of the solid fine particles having the inorganic coating layer described above is subjected to surface modification treatment, so that the surface of the particles is preferably a charged surface.
關於本案發明之固體微粒子附著的線，係於500μm的長度範圍，附著10個~60個粒徑為0.01~100μm的附有無機塗層之固體微粒子為佳。 The line for attaching the solid fine particles in the present invention is preferably in the range of 500 μm, and it is preferable to attach 10 to 60 solid fine particles having an inorganic coating layer having a particle diameter of 0.01 to 100 μm.
關於本案發明之固體微粒子附著的線，上述附有無機塗層之固體微粒子，以選自由鈀塗層鑽石粒子、鎳塗層鑽石粒子、鈦塗層鑽石粒子之1種或2種以上為佳。 In the line to which the solid fine particles of the present invention are attached, the inorganic fine particles having the inorganic coating layer are preferably one or more selected from the group consisting of palladium-coated diamond particles, nickel-coated diamond particles, and titanium-coated diamond particles.
固體微粒子附著的線之製造方法：於製造關於上述本案發明之固體微粒子附著的線，可採用，包含以下的步驟a~步驟d為特徵之製造方法為佳。 A method for producing a solid microparticle-attached line: a method for producing a solid microparticle-attached line according to the above invention may be employed, and a method comprising the following steps a to d is preferred.
步驟a.準備於固體微粒子的表面具備無機塗層之附有無機塗層之固體微粒子的步驟。 Step a. A step of preparing an inorganic coating-attached solid fine particle with an inorganic coating on the surface of the solid fine particles.
步驟b.為對附有無機塗層之固體微粒子的表面，付與既定的極性，使用表面改質劑，進行附有無機塗層之固體微粒子之表面改質處理的步驟。 Step b is a step of subjecting the surface of the solid fine particles having the inorganic coating layer to a predetermined polarity, and using a surface modifying agent to perform surface modification treatment of the inorganic fine particle-attached solid fine particles.
步驟c.將施以該表面改質處理之附有無機塗層之固體微粒子，放入鎳鍍液中使之懸浮狀態，藉由電鍍法，施以於線的表面析出鎳的同時，使附有無機塗層之固體微粒子附著的複合鍍，於線的表面形成含有 固體微粒子之鍍鎳層的步驟。 Step c. Applying the surface-modified surface-attached solid fine particles with inorganic coating, placing them in a nickel plating solution to suspend them, and depositing nickel on the surface of the wire by electroplating. Composite plating with inorganic coatings attached to solid particles, formed on the surface of the wire The step of depositing a nickel layer of solid fine particles.
步驟d.於線表面的含有固體微粒子之鍍鎳層上，進行過鍍鎳的步驟。 Step d. The step of nickel plating is performed on the nickel plating layer containing solid fine particles on the surface of the wire.
關於本案發明之固體微粒子附著的線之製造方法，上述線，使用於表面具備無機保護層者為佳。 In the method for producing a solid microparticle-attached line according to the present invention, it is preferred that the above-mentioned thread is used for an inorganic protective layer on the surface.
關於本案發明之固體微粒子附著的線之製造方法，上述步驟b的表面改質劑，包含胺系、非離子系、陽離子系的任意一種界面活性劑之1種以上為佳。 In the method for producing a solid microparticle-attached line according to the present invention, the surface modifier of the step b may preferably contain one or more of any one of an amine-based, non-ionic or cationic surfactant.
此外，關於本案發明之固體微粒子附著的線之製造方法，上述步驟b的表面改質劑，以包含醇胺類及非離子系界面活性劑為佳。 Further, in the method for producing a solid microparticle-attached line according to the present invention, the surface modifier of the above step b is preferably an alcohol amine or a nonionic surfactant.
關於本案發明之固體微粒子附著的線之製造方法，上述固體微粒子，使用粒徑為0.01~100μm者為佳。 In the method for producing a solid microparticle-attached line according to the present invention, it is preferred that the solid fine particles have a particle diameter of 0.01 to 100 μm.
關於本案發明之固體微粒子附著的線之製造方法，於上述步驟d形成之保護鍍鎳層，厚度以0.1~40μm的範圍為佳。 In the method for producing a solid microparticle-attached line according to the present invention, the protective nickel plating layer formed in the above step d preferably has a thickness of 0.1 to 40 μm.
關於本案發明之固體微粒子附著的線之製造方法，上述線，使用直徑為0.02mm~3.0mm者為佳。 In the method for producing a thread for adhering solid fine particles in the invention of the present invention, it is preferable that the above-mentioned thread has a diameter of 0.02 mm to 3.0 mm.
關於本案發明之固體微粒子附著的線，係於線的表面，具備分散含有附有無機塗層之固體微粒子的含有固體微粒子之電鍍鎳層，及於該含有固體微粒子之電鍍鎳層的表面具備保護鍍鎳層。然後，該附有固體微粒子之線，係於500μm的長度的範圍，安定地具備20個以上粒徑為0.01~100μm之附有無機塗層之固體微粒子。結果，可作為線鋸發揮良好的切斷性能，於被切斷對象物的切斷操作時，不容易發生在線外周面的附有無機塗層之固體微粒子的脫落，可長期穩定地使用。 The wire for attaching the solid fine particles in the invention of the present invention is provided on the surface of the wire, and has an electroplated nickel layer containing solid fine particles dispersed with solid fine particles having an inorganic coating layer, and has a surface protected by the nickel plating layer containing the solid fine particles. Nickel plating. Then, the line with the solid fine particles is in the range of 500 μm in length, and stably contains 20 or more solid fine particles with an inorganic coating layer having a particle diameter of 0.01 to 100 μm. As a result, it is possible to exhibit good cutting performance as a wire saw, and it is not easy to cause the inorganic fine particle-attached solid fine particles on the outer peripheral surface of the wire to be cut off during the cutting operation of the object to be cut, and it can be used stably for a long period of time.
此外，關於本案發明之固體微粒子附著的線，在其製造過程，作為附有無機塗層之固體微粒子，藉由使用，預先將該粒子表面，以既定的表面改質劑進行表面改質處理者，可對線的外周面以適度的分散狀態，且均勻地附著附有無機塗層之固體微粒子。 In addition, in the manufacturing process, the solid microparticles attached to the invention are used as a solid microparticle with an inorganic coating, and the surface of the particle is preliminarily modified by a predetermined surface modifier by using it. The outer peripheral surface of the wire may be in a moderately dispersed state, and the solid fine particles with the inorganic coating may be uniformly attached.
然後，關於本案發明之固體微粒子附著的線之製造方法，使用鍍法中，藉由使用預先施以既定的表面改質處理的附有無機塗層之固體 微粒子，可與添加於鍍液中的附有無機塗層之固體微粒子的量成正比地增加對線的附有無機塗層之固體微粒子的附著量，而可控制附著在線表面的附有無機塗層之固體微粒子量。 Then, regarding the method for producing the solid microparticle-attached line of the invention of the present invention, the inorganic coating-attached solid which has been subjected to a predetermined surface modification treatment by using a plating method is used. The microparticles can increase the adhesion amount of the inorganic coating-coated solid microparticles to the line in proportion to the amount of the inorganic coating-attached solid microparticles added to the plating solution, and can control the adhesion of the on-line surface to the inorganic coating. The amount of solid particles in the layer.
1‧‧‧固體微粒子附著的線 1‧‧‧A line of solid microparticle attachment
2‧‧‧線 2‧‧‧ line
3‧‧‧無機保護層(衝擊鍍層) 3‧‧‧Inorganic protective layer (impact coating)
4‧‧‧固體微粒子 4‧‧‧Solid microparticles
5‧‧‧保護鍍鎳層 5‧‧‧Protective nickel plating
圖1係關於本案申請之固體微粒子附著的線的剖面的示意圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a section of a line to which solid particles are attached in the present application.
圖2係表示使用實施例1的鑽石含量5g/L的電鍍液進行電鍍鎳的線表面的狀態的照片。 Fig. 2 is a photograph showing a state in which a wire surface of nickel plating is performed using the plating solution having a diamond content of 5 g/L of Example 1.
圖3係表示使用實施例2的鑽石含量10g/L的電鍍液進行電鍍鎳的線表面的狀態的照片。 Fig. 3 is a photograph showing a state in which a wire surface of nickel plating is performed using a plating solution having a diamond content of 10 g/L of Example 2.
圖4係表示使用實施例3的鑽石含量15g/L的電鍍液進行電鍍鎳的線表面的狀態的照片。 Fig. 4 is a photograph showing a state in which a wire surface of nickel plating is performed using a plating solution having a diamond content of 15 g/L of Example 3.
圖5係表示使用實施例4的鑽石含量10g/L的電鍍液進行電鍍鎳的線表面的狀態的照片。 Fig. 5 is a photograph showing a state in which a wire surface of nickel plating is performed using a plating solution having a diamond content of 10 g/L of Example 4.
圖6係表示使用實施例5的鑽石含量10g/L的電鍍液進行電鍍鎳的線表面的狀態的照片。 Fig. 6 is a photograph showing a state in which a wire surface of nickel plating is performed using a plating solution having a diamond content of 10 g/L of Example 5.
圖7係表示使用比較例1的鑽石含量5g/L的電鍍液進行電鍍鎳的線表面的狀態的照片。 Fig. 7 is a photograph showing a state in which a wire surface of nickel plating is performed using a plating solution having a diamond content of 5 g/L of Comparative Example 1.
在上述圖1中，符號1是表示「固體微粒子附著的線」，符號2是表示「線」，符號3是表示「無機保護層(衝擊鍍層)」，符號4是表示「固體微粒子」，符號5是表示「保護鍍鎳層」。 In the above-mentioned Fig. 1, reference numeral 1 denotes "a line in which solid fine particles adhere", reference numeral 2 denotes "line", reference numeral 3 denotes "inorganic protective layer (impact plating)", and reference numeral 4 denotes "solid fine particle", symbol 5 means "protective nickel plating".
以下、關於本案發明之固體微粒子附著的線和該固體微粒子附著的線之製造方法就滿意的實施的形態說明。 Hereinafter, a method for producing a solid microparticle-attached line of the invention and a method for producing the solid microparticle-attached line will be described as a satisfactory embodiment.
[固體微粒子附著的線的形態] [Form of the line to which solid particles adhere]
首先，說明關於本案發明之固體微粒子附著的線的形態。關於本案發明之固體微粒子附著的線，係在線的外周面固著固體微粒子而成的固體微粒子附著的線。即，關於本發明的固體微粒子附著的線，係於線的表面上分散含有「附有無機塗層之固體微粒子」之含有固體微粒子之電鍍鎳層，及於含有固體微粒子之電鍍鎳層的表面具備保護鍍鎳層者。以下， 分別說明必要的要素及用語。 First, the form of the line to which the solid fine particles of the present invention are attached will be described. The line to which the solid fine particles adhered in the present invention is a line to which solid fine particles are adhered to the outer peripheral surface of the wire. That is, the line to which the solid fine particles of the present invention adhere is a surface of the wire on which the electroplated nickel layer containing the solid particles containing the inorganic coating is dispersed, and the surface of the electroplated nickel layer containing the solid fine particles is dispersed. It has the protection of nickel plating. the following, Explain the necessary elements and terms separately.
<含有固體微粒子之電鍍鎳層> <Electroplated nickel layer containing solid particles>
該含有固體微粒子之電鍍鎳層，係直接接觸披覆在該線的表面者，於電鍍鎳層內分散包含附有無機塗層之固體微粒子。即，鎳成分，係發揮作為使附有無機塗層之固體微粒子，固定於線表面之粘合劑的作用。該含有固體微粒子之電鍍鎳層所包含的鎳成分，並不單只是表面披覆，與後述之線具有良好的沾濕性，且發揮化學親和性。因此，於線表面以電解法設置之電解鎳層，具備良好的密著性。然後，用於該含有固體微粒子之電鍍鎳層之構成之鎳鍍液，可使用純鎳鍍液、鎳合金(鎳-磷、鎳-鈷、鎳-鋅等的鎳基合金)鍍液。 The electroplated nickel layer containing the solid fine particles is directly contacted with the surface coated on the surface of the wire, and the solid fine particles having the inorganic coating layer are dispersed in the electroplated nickel layer. In other words, the nickel component functions as a binder which fixes the solid fine particles having the inorganic coating layer to the surface of the wire. The nickel component contained in the electroplated nickel layer containing the solid fine particles does not only have a surface coating, but also has a good wettability with a line to be described later, and exhibits chemical affinity. Therefore, the electrolytic nickel layer provided on the surface of the wire by electrolysis has good adhesion. Then, as the nickel plating solution for the nickel-plated layer containing the solid fine particles, a pure nickel plating solution or a nickel alloy (nickel-phosphorus, nickel-cobalt, nickel-zinc-based nickel-based alloy) plating solution can be used.
線：用於本案申請的線，只要是可於其表面電鍍，而具有一定的強度者，並無特別限制，可按照使用的用途適宜選擇。如此之線，可舉例如，鋼琴線等的鋼線、鎢絲、鉬線、不鏽鋼線等。 Line: The line used for the application of the present invention is not particularly limited as long as it can be plated on the surface thereof, and can be appropriately selected according to the intended use. Such a line may, for example, be a steel wire such as a piano wire, a tungsten wire, a molybdenum wire, or a stainless steel wire.
該固體微粒子附著的線的芯材的線的直徑，本來，不應被限定，可按照用途，適宜選擇。但是，考慮如此之固體微粒子附著的線的用途的大部分係「線鋸」，則該線的直徑以0.02mm~3.0mm為佳。作用作為線鋸之固體微粒子附著的線的情形，線的直徑未滿0.02mm，則在於後述之使用既定的粒徑的附有無機塗層之固體微粒子之製造方法，有難以對線表面有效地附著附有無機塗層之固體微粒子之傾向而不佳。另一方面，該線的直徑的上限，由於因用途不同而異，故以大約的標準決定。例如，用於切斷矽晶圓的固體微粒子附著的線之情形，以0.8mm為上限。該線的直徑超過0.8mm，則由被切斷物的切斷精度的觀點來看，並不一定需要使用線鋸，埋沒了線鋸的必要性而不佳。再者，將固體微粒子附著的線使用於太陽能電池的矽晶圓的切斷時，使用直徑0.06mm~0.23mm的線，最符合市場要求。然後，用於切斷鋼筋混凝土、構造用鋼等的構造物的固體微粒子附著的線之情形，以3.0mm為上限。該線的直徑超過3.0mm，則失去作為線的柔軟性，難以操作。 The diameter of the wire of the core material of the wire to which the solid fine particles are attached is not limited as it is, and may be appropriately selected depending on the use. However, in consideration of the use of such a wire for the attachment of such solid particles, the wire has a diameter of 0.02 mm to 3.0 mm. When the diameter of the wire is less than 0.02 mm, the diameter of the wire is less than 0.02 mm, and it is difficult to apply the solid particle-attached solid fine particles using a predetermined particle diameter to be described later. The tendency to attach solid microparticles with an inorganic coating is not good. On the other hand, the upper limit of the diameter of the wire varies depending on the application, and is determined by an approximate standard. For example, in the case of a line for cutting the solid particles attached to the tantalum wafer, the upper limit is 0.8 mm. When the diameter of the wire exceeds 0.8 mm, it is not necessary to use a wire saw from the viewpoint of the cutting accuracy of the object to be cut, and the necessity of burying the wire saw is not preferable. Further, when the wire to which the solid fine particles are attached is used for cutting the tantalum wafer of the solar cell, a wire having a diameter of 0.06 mm to 0.23 mm is used, which is most suitable for the market. Then, in the case of cutting a line in which solid fine particles adhere to a structure such as reinforced concrete or structural steel, the upper limit is 3.0 mm. When the diameter of the wire exceeds 3.0 mm, the flexibility as a thread is lost and it is difficult to handle.
然後，關於本案發明之固體微粒子附著的線，使用於上述線的表面具備無機保護層者為佳。藉由於線的表面，存在無機保護層，可防止線的表面在於加工途中發生微裂紋，防止發生斷線，且，可進行防止線 的腐蝕。此外，根據無機保護層的種類，亦可將後述的固體微粒子的附著狀態穩定化。該無機保護層，可使用鎳、鎳合金(Ni-Co、Ni-Sn、Ni-Zn)、Cu、銅合金(Cu-Zn、Cu-Sn)等。 Then, it is preferable that the line to which the solid fine particles of the present invention are attached is provided with an inorganic protective layer on the surface of the above-mentioned wire. By the surface of the wire, there is an inorganic protective layer, which prevents the surface of the wire from being microcracked during processing, preventing breakage, and preventing the wire from being formed. Corrosion. Further, depending on the type of the inorganic protective layer, the adhesion state of the solid fine particles to be described later can be stabilized. As the inorganic protective layer, nickel, a nickel alloy (Ni-Co, Ni-Sn, Ni-Zn), Cu, a copper alloy (Cu-Zn, Cu-Sn), or the like can be used.
固體微粒子：說明使用於本案申請之使用於作為附有無機塗層之固體微粒子之芯材之固體微粒子。在此所述固體微粒子，可按照固體微粒子附著的線的用途適宜選擇，可舉例如氧化鈰、氧化矽(石英、溶融二氧化矽等)、氧化鋁、碳化矽、窒化矽、氧化鋯、鑽石等的微粒子等。特別是，將固體微粒子附著的線用於作為線鋸用於切斷矽晶圓等時，使用鑽石粒子為佳。 Solid Microparticles: Describes the solid microparticles used in the present application as a core material with solid particles attached to an inorganic coating. The solid fine particles described herein can be appropriately selected according to the use of the line to which the solid fine particles are attached, and examples thereof include cerium oxide, cerium oxide (quartz, molten cerium oxide, etc.), aluminum oxide, cerium carbide, cerium lanthanum, zirconia, and diamond. Such as microparticles. In particular, when a wire to which solid fine particles are attached is used as a wire saw for cutting a tantalum wafer or the like, it is preferable to use diamond particles.
該固體微粒子，使用粒徑以0.01~100μm者為佳。固體微粒子的粒徑未滿0.01μm時，固體微粒子附著的線的表面變的過於滑潤，不僅於線鋸的用途，在其他的用途，亦會埋沒對線附著固體微粒子之意義而不佳。另一方面，固體微粒子的粒徑超過100μm時，即使使用關於本案發明之線的最大直徑的0.8mm的線，有難以使固體微粒子維持均勻的分散性而附著於該線表面的傾向，且並不存在如此之市場要求。特別是以切斷太陽能電池用的矽晶圓為目的所使用的固體微粒子附著的線之情形，對直徑0.08~0.2mm的線使用粒徑4~40μm的固體微粒子，顯示適於線鋸用途的良好的切斷性能，且附著於線表面的固體微粒子在切斷時的脫落少，可使線鋸的長壽化而更佳。 The solid fine particles are preferably those having a particle diameter of 0.01 to 100 μm. When the particle diameter of the solid fine particles is less than 0.01 μm, the surface of the wire to which the solid fine particles adhere is too smooth, which is not only useful for the use of the wire saw, but also has no significance for burying the solid particles attached to the wire for other uses. On the other hand, when the particle diameter of the solid fine particles exceeds 100 μm, even if a line having a maximum diameter of 0.8 mm of the wire of the present invention is used, it is difficult to maintain the uniform dispersibility of the solid fine particles and adhere to the surface of the wire, and There is no such market requirement. In particular, in the case of a line in which solid fine particles are used for the purpose of cutting a tantalum wafer for a solar cell, solid particles having a particle diameter of 4 to 40 μm are used for a wire having a diameter of 0.08 to 0.2 mm, and are suitable for use in a wire saw. Good cutting performance, and the solid fine particles adhering to the surface of the wire are less likely to fall off during cutting, and the life of the wire saw can be improved.
附有無機塗層之固體微粒子：在此所述的附有無機塗層之固體微粒子，係於固體微粒子的表面上，具有由金屬成分構成的無機塗層者。然後，該無機塗層的構成成分，按照固體微粒子附著的線的用途，可適宜選擇使用。在此所述的附有無機塗層之固體微粒子，更具體地例示，則可假定附有鈀塗層之固體微粒子、附有鎳塗層之固體微粒子、附有鈦塗層之固體微粒子等。具有該等無機塗層的附有無機塗層之固體微粒子，與以鍍法形成之鎳或鎳合金的析出成分的沾濕性佳，可得良好的密著性。 Solid microparticles with an inorganic coating: The inorganic microparticles attached to the inorganic coating described herein are attached to the surface of the solid microparticles and have an inorganic coating composed of a metal component. Then, the constituent component of the inorganic coating layer can be appropriately selected and used depending on the use of the line to which the solid fine particles adhere. The inorganic fine particle-attached solid fine particles described herein, more specifically exemplified, may be assumed to have a solid particle attached with a palladium coating, a solid fine particle with a nickel coating, a solid fine particle with a titanium coating, and the like. The inorganic fine particle-attached solid fine particles having the inorganic coating layer have good wettability with the precipitation component of the nickel or nickel alloy formed by the plating method, and good adhesion can be obtained.
該等附有無機塗層之固體微粒子，均勻地分散存在於含有固體微粒子之電鍍鎳層之中。該附有無機塗層之固體微粒子，亦可藉由預先，以表面改質劑施以表面改質處理，使附有無機塗層之固體微粒子之表面成為帶電表面，對粒子表面付與既定的極性為佳。此時之附有鈀塗層之固體 微粒子，按照線的極化狀態，亦可選擇使用非離子粒子、陽離子粒子之任一的帶電狀態。即，顯示具體的一例，則電鍍鎳時，將線分極為陰極時，對該鍍液，使附有無機塗層之固體微粒子的粒子表面帶電成相反的正極。藉由如此之附有無機塗層之固體微粒子之表面改質處理，在於以下的固體微粒子附著的線之製造方法的電鍍時，固體微粒子對線的表面均勻地分散附著，與該鍍液中的附有無機塗層之固體微粒子量成正比地，可得固體微粒子附著的線的附有無機塗層之固體微粒子的附著量。關於該表面改質處理，將於後面的製造方法進一步說明。 The inorganic fine particles attached with the inorganic coating are uniformly dispersed in the electroplated nickel layer containing the solid fine particles. The solid microparticles with the inorganic coating may be surface-modified by a surface modifier in advance, so that the surface of the solid microparticles with the inorganic coating becomes a charged surface, and the surface of the particles is given a predetermined surface. The polarity is better. Palladium coated solid at this time For the microparticles, depending on the polarization state of the line, a charged state of either the nonionic particles or the cationic particles may be selected. That is, in a specific example, when the nickel is electroplated, when the line is extremely cathode, the surface of the particles coated with the inorganic fine particles is charged to the opposite positive electrode. The surface modification treatment of the solid fine particles with the inorganic coating layer is performed in the following method of manufacturing the solid microparticle-attached line, and the solid fine particles are uniformly dispersed on the surface of the wire, and in the plating solution. The amount of the solid fine particles with the inorganic coating is proportional to the amount of the inorganic fine particle-attached solid fine particles attached to the line to which the solid fine particles are attached. This surface modification treatment will be further described in the subsequent production method.
<保護鍍鎳層> <Protective nickel plating>
然後，上述保護鍍鎳層，係設於包含上述固體微粒子之含有固體微粒子之電鍍鎳層的表面上，構成固體微粒子附著的線的最外層者。因此，保護鍍鎳層，係有防止上述含有固體微粒子之電鍍鎳層的固體微粒子脫落的作用。 Then, the protective nickel plating layer is provided on the surface of the electroplated nickel layer containing the solid fine particles including the solid fine particles, and constitutes the outermost layer of the line to which the solid fine particles adhere. Therefore, the protection of the nickel plating layer serves to prevent the solid fine particles of the electroplated nickel layer containing the solid fine particles from falling off.
在此所述「保護鍍鎳層」，以使用純鎳鍍液、鎳合金(鎳-磷、鎳-鈷、鎳-鋅等的鎳基合金)鍍液構成為佳。該「保護鍍鎳層」所包含的鎳成分，並不單只是表面披覆，發揮與上述「含有固體微粒子之電鍍鎳層」良好的沾濕性，且即使底層有因固體微粒子之凹凸，亦可成為薄且均勻的投擲性良好的披膜。 Here, the "protective nickel plating layer" is preferably a plating solution using a pure nickel plating solution or a nickel alloy (nickel-phosphorus, nickel-cobalt, nickel-zinc or the like). The nickel component contained in the "protective nickel plating layer" does not only have a surface coating, but also exhibits good wettability with the above-mentioned "nickel plating layer containing solid fine particles", and even if the underlying layer has irregularities due to solid particles, It becomes a thin and uniform drape with good throwing.
藉由採用以上所說明，於線表面，分散含有附有鈀塗層之固體微粒子之含有固體微粒子之電鍍鎳層，及於其表面採用具備保護鍍鎳層之固體微粒子附著的線，可有效地防止附著在線的固體微粒子的脫落。藉此，可得可靠度高，且可實現長期使用之固體微粒子附著的線。 By using the above-described method, an electroplated nickel layer containing solid fine particles containing solid particles of a palladium-coated layer is dispersed on the surface of the wire, and a line having solid microparticles having a protective nickel plating layer adhered to the surface thereof can be effectively used. Prevents the shedding of solid particles attached to the wire. Thereby, a line which is highly reliable and can adhere to the solid particles to be used for a long period of time can be obtained.
[固體微粒子附著的線的製造形態] [Manufacturing form of a line to which solid particles adhere]
接著，說明關於本案發明之固體微粒子附著的線之製造方法。 Next, a method of manufacturing the wire to which the solid fine particles of the present invention are attached will be described.
線的潔淨化處理：用於製造關於本案發明之固體微粒子附著的線的線，首先，將表面脫脂，清洗為佳。關於此時之脫脂方法，並無特別限定，可使用例如，酸浸漬、溶劑脫脂、乳化劑脫脂、鹼性脫脂等。再者，按照必要，亦可使用電解脫脂。 The cleaning treatment of the wire: a wire for producing a wire attached to the solid fine particles of the present invention. First, the surface is degreased and washed. The degreasing method at this time is not particularly limited, and for example, acid immersion, solvent degreasing, emulsifier degreasing, alkaline degreasing, and the like can be used. Further, electrolytic degreasing can also be used as necessary.
然後，關於本案發明之固體微粒子附著的線之製造方法，其 特徵在於：包含以下步驟a~步驟d。 Then, a method for producing a line in which solid fine particles adhere to the invention of the present invention is The feature is that it includes the following steps a~step d.
步驟a：於此步驟，準備於固體微粒子的表面具備無機塗層之附有無機塗層之固體微粒子。因此，準備附有無機塗層之固體微粒子之芯材(上述氧化鈰、氧化矽(石英、溶融二氧化矽等)、氧化鋁、碳化矽、氧化鋯、鑽石、聚四氟乙烯等的微粒子。)，於該粒子表面具有由金屬成分構成之無機塗層者，附有鈀塗層之固體微粒子、附有鎳塗層之固體微粒子、附有鈦塗層之固體微粒子等。使用相當於該等附有無機塗層之固體微粒子之市售品亦無妨。 Step a: In this step, the inorganic fine particle-attached solid fine particles having an inorganic coating are prepared on the surface of the solid fine particles. Therefore, a core material (the above-mentioned cerium oxide, cerium oxide (quartz, molten cerium oxide, etc.), alumina, tantalum carbide, zirconia, diamond, polytetrafluoroethylene, or the like) is prepared. The inorganic coating layer composed of a metal component on the surface of the particle, the solid microparticles coated with a palladium coating, the solid microparticles with a nickel coating, and the solid microparticles with a titanium coating. It is also possible to use a commercial product equivalent to such solid particles with an inorganic coating.
但是，附有無機塗層之固體微粒子之中，關於附有鈀塗層之固體微粒子，以如下方法將固體微粒子的表面塗層鈀為佳。 However, among the solid fine particles with an inorganic coating layer, it is preferable to coat the surface of the solid fine particles with palladium as a solid fine particle having a palladium coating.
第1鈀塗層方法，係「於固體微粒子的粒子表面，藉由使鈀與錫共析之後，僅將固體微粒子表面的錫分解去除，作成只有鈀存在於固體微粒子的表面上的狀態的方法。」。關於此方法，具體舉一例說明。可使用以鈀．錫膠體觸媒為主要成分的溶液，作為含有錫與鈀的溶液。將如此之溶液中，浸漬固體微粒子，則鈀．錫膠體觸媒將吸附於固體微粒子的表面。此時，鈀的吸附量，每固體微粒子1g當量以0.1~20mg為佳。該鈀吸附量，每固體微粒子1g當量未滿0.1mg，則鈀對固體微粒子的粒子表面的吸附量少，無法充分地得到與以鍍法形成鎳或鎳合金的析出成分的沾濕性，無法得到良好的密著性而不佳。另一方面，該鈀吸附量，即使以每固體微粒子1g當量超過20mg者，鎳與固體微粒子的共析效果飽和，無法提升而不佳。該鈀吸附量，每固體微粒子1g當量由超過10mg附近，鎳與固體微粒子的共析效果，只能緩慢地提升，故較佳的鈀吸附量，於每固體微粒子1g當量為0.1~10mg。 The first palladium coating method is a method in which only the surface of the solid fine particles is co-deposited with palladium and tin, and only the tin on the surface of the solid fine particles is decomposed and removed, and only palladium is present on the surface of the solid fine particles. "." An example of this method will be described. Can be used with palladium. A solution in which a tin colloid catalyst is a main component is used as a solution containing tin and palladium. In such a solution, impregnating solid particles, then palladium. The tin colloid catalyst will adsorb to the surface of the solid particles. In this case, the adsorption amount of palladium is preferably 0.1 to 20 mg per 1 g equivalent of the solid fine particles. When the amount of palladium adsorbed is less than 0.1 mg per solid equivalent of fine particles, the amount of adsorption of palladium on the surface of the particles of the solid fine particles is small, and the wettability of the precipitated component of nickel or nickel alloy formed by plating cannot be sufficiently obtained. It is not good to get good adhesion. On the other hand, even if the amount of the palladium adsorbed exceeds 20 mg per 1 g of the solid fine particles, the effect of the eutectoid precipitation of nickel and solid fine particles is saturated, which is not preferable. The palladium adsorption amount is more than 10 mg per solid particle, and the effect of the eutectoid effect of nickel and solid fine particles can only be gradually increased. Therefore, the preferred palladium adsorption amount is 0.1 to 10 mg per 1 g equivalent of the solid fine particles.
接著，將於粒子表面，吸附鈀．錫膠體的固體微粒子，與氯、硫酸、硼氟酸等的酸接觸，邊將錫成分分解去除，使鈀微粒子析出在固體微粒子表面。於此階段，成為在固體微粒子的粒子表面形成鈀塗層的狀態。 Next, the palladium will be adsorbed on the surface of the particle. The solid particles of the tin colloid are in contact with an acid such as chlorine, sulfuric acid or borofluoric acid, and the tin component is decomposed and removed to precipitate palladium particles on the surface of the solid fine particles. At this stage, a state in which a palladium coating layer is formed on the surface of the particles of the solid fine particles is obtained.
第2鈀塗層方法，係「將固體微粒子浸漬於錫溶液既定時間，使錫在固體微粒子的表面析出，接著浸漬於鈀溶液既定時間，利用錫與鈀的置換反應，於粒子表面析出鈀的方法。」。 In the second palladium coating method, "the solid fine particles are immersed in the tin solution for a predetermined period of time, and the tin is deposited on the surface of the solid fine particles, and then immersed in the palladium solution for a predetermined period of time, and the palladium is precipitated on the surface of the particles by a substitution reaction of tin and palladium. method.".
上述第1鈀塗層方法及第2鈀塗層方法，均為確實地去除包 含於該鈀塗層之錫，亦可於事後，使用氯、硫酸、硼氟酸、羧酸、羥基羧酸、芳香族羧酸等的酸性溶液去除。 The first palladium coating method and the second palladium coating method are all positively removed The tin contained in the palladium coating may be removed afterwards using an acidic solution of chlorine, sulfuric acid, borofluoric acid, carboxylic acid, hydroxycarboxylic acid or aromatic carboxylic acid.
再者，第1鈀塗層方法及第2鈀塗層方法，僅為例示，在關於本案發明之發明，只要可以鈀塗層披覆固體微粒子的表面即可，寫明並不應解釋為限定於該等方法。 In addition, the first palladium coating method and the second palladium coating method are merely illustrative. In the invention of the present invention, as long as the surface of the solid fine particles can be coated with a palladium coating, the description should not be construed as limiting. In these methods.
步驟b.：於該步驟，係將在於上述步驟a之附有無機塗層之固體微粒子的表面，與表面改質劑接觸，使之帶電成既定的極性的表面改質處理步驟。該步驟，係於先前的固體微粒子附著的線的製造所沒有的步驟。先前的固體微粒子附著的線之製造方法，難以使固體微粒子有效地附著在線。因此，本案發明者們，專心進行研究的結果，發現在固體微粒子的表面上設置無機塗層之後，預先藉由表面改質劑施以表面改質處理，使該表面的極性穩定化。結果，在於含有固體微粒子之電鍍鎳層形成步驟，可任意地控制附著在線表面的固體微粒子的附著量，可顯著地增加附著量，且可均勻地分散。 Step b.: In this step, the surface of the solid microparticles attached with the inorganic coating in the above step a is brought into contact with the surface modifying agent to be charged into a surface modification step of a predetermined polarity. This step is a step not in the manufacture of the previous line of solid particle attachment. In the method of manufacturing the line in which the solid particles are attached, it is difficult to effectively adhere the solid particles to the wire. Therefore, as a result of intensive research, the inventors of the present invention found that after the inorganic coating layer is provided on the surface of the solid fine particles, the surface modification treatment is applied in advance by the surface modifying agent to stabilize the polarity of the surface. As a result, in the step of forming the electroplated nickel layer containing the solid fine particles, the amount of adhesion of the solid fine particles adhering to the surface of the wire can be arbitrarily controlled, the amount of adhesion can be remarkably increased, and the dispersion can be uniformly dispersed.
具體而言，在於後述的步驟c(含有固體微粒子之電鍍鎳層形成步驟)的鍍液中，將線分極化為陰極時，將附有無機塗層之固體微粒子的表面，預先施以帶電於正極之處理。想到藉由如此，可使固體微粒子容易附著在後面的線的表面。此係，於電鍍時，對分極於陰極的線，使固體微粒子的表面帶電於正極，藉由將固體微粒子本身帶正的電荷的狀態穩定化，於電鍍時，使固體微粒子容易被線吸引。 Specifically, in the plating solution of the step c (electroplated nickel layer forming step containing solid fine particles) to be described later, when the line is polarized into a cathode, the surface of the solid fine particles with the inorganic coating is charged in advance. The treatment of the positive electrode. It is thought that by this, the solid fine particles can be easily attached to the surface of the subsequent line. In this case, at the time of electroplating, the surface of the solid microparticles is charged to the positive electrode, and the solid microparticles themselves are stabilized in a state of positive charge, so that the solid microparticles are easily attracted by the wire during electroplating.
此時之表面改質處理，可由將固體微粒子，浸漬於表面處理劑的方法、將該表面處理劑噴霧在固體微粒子表面的方法等，選擇最合適的方法實施。採用浸漬法，則將固體微粒子投入含有表面改質劑的處理槽，邊攪拌，浸漬處理既定時間。然後，結束既定時間的處理，將固體微粒子由處理槽分離採取，水洗，乾燥。 The surface modification treatment at this time can be carried out by selecting a method in which solid fine particles are immersed in a surface treatment agent, a method of spraying the surface treatment agent on the surface of the solid fine particles, and the like, and selecting an optimum method. In the impregnation method, the solid fine particles are introduced into a treatment tank containing a surface modifier, stirred, and immersed for a predetermined period of time. Then, the treatment for a predetermined period of time is completed, and the solid fine particles are separated from the treatment tank, washed with water, and dried.
於形成該含有固體微粒子之電鍍鎳層時，使附有無機塗層之固體微粒子附著於線表面，同時由帶正電荷的鎳離子析出鎳成分。因此，使用於該表面改質處理之表面改質劑，需要使用可對附有無機塗層之固體微粒子之表面附與正的極性而穩定化者。如此之界面改質劑，使用包含胺系界面活性劑、非離子系界面活性劑或陽離子系界面活性劑之任意一個界 面活性劑為佳，其中採用含有醇胺類的非離子系界面活性劑為佳。如此之表面改質劑，藉由使該表面改質劑與固體微粒子接觸既定時間，可使附有無機塗層之固體微粒子的表面，有效地帶電於正極，可圖謀帶電於正極的狀態的穩定化。 When the electroplated nickel layer containing the solid fine particles is formed, the solid fine particles with the inorganic coating are attached to the surface of the wire, and the nickel component is precipitated by the positively charged nickel ions. Therefore, the surface modifier used for the surface modification treatment needs to be stabilized by applying a positive polarity to the surface of the solid fine particles with an inorganic coating. Such an interface modifier uses any one of an amine-based surfactant, a nonionic surfactant, or a cationic surfactant. A surfactant is preferred, and a nonionic surfactant containing an alcoholamine is preferred. When the surface modifier is brought into contact with the solid fine particles for a predetermined period of time, the surface of the solid fine particles with the inorganic coating can be effectively charged to the positive electrode, and the state of charging the positive electrode can be stabilized. Chemical.
步驟c.：此步驟，係藉由電鍍法，於線的表面形成含有無機塗層之固體微粒子之電鍍鎳層的複合鍍敷之含有固體微粒子之電鍍鎳層的形成步驟。於以下敘述在此施以含有固體微粒子之電鍍鎳的方法。 Step c.: This step is a step of forming a nickel-plated layer containing solid fine particles by composite plating of an electroplated nickel layer containing inorganic fine particles of solid particles on the surface of the wire by electroplating. A method of applying electroplated nickel containing solid fine particles here is described below.
首先，敘述關於線。在此，使用的線，使用於其表面具備無機保護層者為佳。構成如上所述之無機保護層的金屬成分，可使用鎳、鎳合金(Ni-Co、Ni-Sn、Ni-Zn)、Cu、銅合金(Cu-Zn、Cu-Sn)等，但是考慮耐腐蝕性能及固體微粒子的附著穩定性，使用鎳或鎳合金最佳。然後，由該鎳或鎳合金組成的無機保護層，使用所謂「衝擊鍍法」形成為佳。該衝擊鍍，係使用低離子濃度的電解液，以高的電流密度進行短時間鍍敷處理，形成厚度0.1μm以下的薄鍍層者。此時的電流供給方法，當然可用單純的直流電流進行鍍敷，惟為防止因使用高電流密度降低品質，採用反覆通電狀態與電流停止狀態的「脈衝鍍法」為佳。採用脈衝鍍時，關於脈衝波形，並無特段的限定，可使用方形波．三角波等。然後，關於整流模式，並無限定，可使用半波整流．全波整流。然後，頻率200Hz~2000Hz、Duty Ratio(on：20、off：80)、電流密度3A/dm2~10A/dm2的條件等。 First, the narrative is about the line. Here, the wire to be used is preferably used for an inorganic protective layer on its surface. As the metal component constituting the inorganic protective layer as described above, nickel, a nickel alloy (Ni-Co, Ni-Sn, Ni-Zn), Cu, a copper alloy (Cu-Zn, Cu-Sn), or the like can be used, but it is considered to be resistant. Corrosion properties and adhesion stability of solid particles are best used with nickel or nickel alloys. Then, the inorganic protective layer composed of the nickel or the nickel alloy is preferably formed by a so-called "impact plating method". This impact plating is performed by using a low ion concentration electrolyte solution and performing a short-time plating treatment at a high current density to form a thin plating layer having a thickness of 0.1 μm or less. The current supply method at this time can of course be plated with a simple direct current, and it is preferable to prevent the "pulse plating method" of the reverse energization state and the current stop state by using a high current density to reduce the quality. When using pulse plating, there is no special limitation on the pulse waveform, and a square wave can be used. Triangle wave and so on. Then, regarding the rectification mode, there is no limitation, and half-wave rectification can be used. Full wave rectification. Then, the frequency is 200 Hz to 2000 Hz, the duty ratio (on: 20, off: 80), the current density of 3 A/dm 2 to 10 A/dm 2 , and the like.
以下，舉出使用於衝擊鍍的代表的浴組成。作為一例，於鎳衝擊鍍之情形，可使用後述之磺胺酸系鎳鍍浴，瓦特浴。氰化銅衝擊鍍之情形，可使用含有氰化銅20~35g/L、氰化鈉37~60g/L、氫氧化鉀3~5g/L、洛捷爾鹽10~20g/L的電解液。焦磷酸銅衝擊鍍之情形，可使用含有焦磷酸銅16g/L，焦磷酸鉀120g/L、草酸鉀10g/L的電解液。 Hereinafter, representative bath compositions used for impact plating will be mentioned. As an example, in the case of nickel impact plating, a sulfaic acid-based nickel plating bath to be described later and a Watt bath can be used. In the case of copper cyanide impact plating, an electrolyte 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 Loiter salt can be used. . In the case of copper pyrophosphate impact 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.
接著，作為形成該含有固體微粒子之電鍍鎳層的鍍液，使用於上述步驟b施以表面改質處理之附有無機塗層之固體微粒子，懸浮於包含鎳成分的鍍液中者。該鍍液，亦可使用對市售的鎳電鍍液，將於步驟b作表面改質處理之附有無機塗層之固體微粒子懸浮者，亦可將適用於鍍鎳的瓦特浴，磺胺酸浴等建浴，將於步驟b作表面改質處理之附有無機塗層之固體微粒子懸浮者。例如，此時的鎳鍍液，並無特段的限定，亦可採用 可平滑鍍鎳的浴組成，電解條件。作為一例，以下列舉幾個鎳鍍浴及鍍敷條件。 Next, as a plating solution for forming the electroplated nickel layer containing the solid fine particles, the inorganic fine particle-attached solid fine particles subjected to the surface modification treatment in the above step b are suspended in the plating solution containing the nickel component. The plating solution may also be a commercially available nickel plating solution, a surface-modified material of the inorganic coating-attached solid microparticle suspension, or a nickel-plated Watt bath, sulfamic acid bath. After the bath is built, the solid particle suspension with the inorganic coating will be surface-modified in step b. For example, the nickel plating solution at this time has no special limitation and can also be used. Smooth nickel plating bath composition, electrolysis conditions. As an example, several nickel plating baths and plating conditions are listed below.
使用磺胺酸系鎳鍍浴，則可採用磺胺酸鎳．4水和物200~800g/L，氯化鎳．6水和物1~10g/L，硼酸20~50g/L，pH3~5的鍍鎳組成等。 When using a sulfaic acid nickel plating bath, nickel sulfamate can be used. 4 water and material 200 ~ 800g / L, nickel chloride. 6 water and material 1 ~ 10g / L, boric acid 20 ~ 50g / L, pH 3 ~ 5 nickel plating composition.
使用瓦特浴系的鎳鍍浴，則可採用硫酸鎳．7水和物200~500g/L、氯化鎳．7水和物10~100g/L、硼酸20~50g/L、pH3~5的鍍鎳組成等。 Nickel sulfate can be used in the nickel plating bath of the Watt bath system. 7 water and material 200 ~ 500g / L, nickel chloride. 7 water and material 10 ~ 100g / L, boric acid 20 ~ 50g / L, pH 3 ~ 5 nickel plating composition.
用於形成含有固體微粒子之電鍍鎳層的鍍液的附有無機塗層之固體微粒子的含量，考慮在線的表面上，與鎳同時共析之固體微粒子量的關係，可採用任意添加量。例如，欲得線鋸用途之固體微粒子附著的線，則按照被切斷體的種類，使固體微粒子的含量為4g/l~40g/l程度為佳。固體微粒子的含量未滿4g/l，則將成為不具有良好的切斷性能的線鋸。另一方面，固體微粒子的含量超過40g/l，則附著在線表面的固體微粒子量過剩，難以使固體微粒子均勻地附著於線的表面而不佳。 The content of the inorganic fine particle-attached solid fine particles for forming the plating solution for the electroplated nickel layer containing the solid fine particles can be arbitrarily added in consideration of the relationship between the amount of solid fine particles simultaneously co-evolved with nickel on the surface of the wire. For example, in order to obtain a line to which the solid fine particles of the wire saw are attached, the content of the solid fine particles is preferably 4 g/l to 40 g/l, depending on the type of the cut body. When the content of the solid fine particles is less than 4 g/l, it becomes a wire saw which does not have good cutting performance. On the other hand, when the content of the solid fine particles exceeds 40 g/l, the amount of solid fine particles adhering to the wire surface is excessive, and it is difficult to uniformly attach the solid fine particles to the surface of the wire.
然後，使用懸浮上述固體微粒子的鍍液，適用一般的鍍敷條件，在線的表面使固體微粒子與鎳共析。此時對線的500μm長，使固體微粒子共析附著10個~60個，更佳的是20個~50個為佳。該固體微粒子，未滿10個時，由於作為線鋸的切斷性能會下降而不佳。另一方面，固體微粒子超過60個，則在線鋸的操作時容易使固體微粒子脫落，有使被切斷物的切斷面變粗的傾向而不佳。藉此，可於線的表面，形成以分散附有鈀塗層之固體微粒子的形式含有之含有固體微粒子之電鍍鎳層。 Then, using a plating solution in which the above solid fine particles are suspended, general plating conditions are applied, and the surface of the wire is used to eutect the solid fine particles with nickel. At this time, the line is 500 μm long, and the solid particles are subjected to eutectoid deposition of 10 to 60, and more preferably 20 to 50. When the number of the solid fine particles is less than ten, the cutting performance as a wire saw may be lowered. On the other hand, when the number of the solid fine particles exceeds 60, the solid fine particles are liable to fall off during the operation of the wire saw, and the cut surface of the cut object tends to be coarse. Thereby, an electroplated nickel layer containing solid fine particles contained in the form of dispersed solid particles containing a palladium coating can be formed on the surface of the wire.
步驟d.此步驟，係對上述步驟c所得之含有固體微粒子之電鍍鎳層的表面，進一步進行鍍鎳的保護鍍鎳層形成步驟。在此，施以鍍鎳的手法，採用電鍍法，由生產速度的觀點為佳。於此步驟d使用的鍍液，亦可使用市售的鎳鍍浴，亦可使用如上述步驟c所詳述，使用瓦特浴或磺胺酸浴等自己調製者，亦無妨。 Step d. This step is a step of forming a nickel-plated protective nickel plating layer on the surface of the electroplated nickel layer containing the solid fine particles obtained in the above step c. Here, the nickel plating method is applied, and the electroplating method is used, and the viewpoint of the production speed is preferable. The plating solution used in the step d may be a commercially available nickel plating bath, or may be prepared by using a Watt bath or a sulfamic acid bath as described in the above step c.
然後，將形成含有固體微粒子之電鍍鎳層之上述線浸漬於液溫30~60℃的鎳鍍液，將該線分極於陰極，於含有固體微粒子之電鍍鎳層上形成所期望的厚度的保護鍍鎳層。在此，鎳鍍液的液溫未滿30℃時，可含 於鍍液中的飽和鎳量會下降，而使鍍敷速度降低而招致工業生產性的下降的同時，有使形成之保護鍍鎳層的表面平滑性下降的傾向而不佳。另一方面，鎳鍍液的液溫超過60℃，則由於難以使用氯乙烯配管，故製造設備的構成材料的限制變大，且鍍液的水分的蒸發速度變快而使鍍液的組成變動變大，故難以穩定的鍍敷操作而不佳。關於其他的鍍敷條件，只要可平滑的鍍鎳，並無特段的限定。 Then, the wire forming the electroplated nickel layer containing the solid fine particles is immersed in a nickel plating solution having a liquid temperature of 30 to 60 ° C, and the wire is divided into a cathode to form a desired thickness on the electroplated nickel layer containing the solid fine particles. Nickel plating. Here, when the liquid temperature of the nickel plating solution is less than 30 ° C, it may be contained The amount of saturated nickel in the plating solution is lowered, and the plating speed is lowered to cause a decrease in industrial productivity, and the surface smoothness of the formed protective nickel plating layer tends to be lowered. On the other hand, when the liquid temperature of the nickel plating solution exceeds 60 ° C, it is difficult to use a vinyl chloride pipe, so that the limitation of the constituent materials of the production equipment is increased, and the evaporation rate of the water in the plating solution is increased to change the composition of the plating solution. It becomes larger, so it is difficult to stabilize the plating operation. Regarding other plating conditions, there is no particular limitation as long as it can be smoothly plated with nickel.
以該步驟d形成之保護鍍鎳層，係設於含有固體微粒子之電鍍鎳層之外表面者，位於固體微粒子附著的線的最外層者。因此，保護鍍鎳層，可有效地防止包含於含有固體微粒子之電鍍鎳層的固體微粒子的脫落。該保護鍍鎳層，以0.1~40μm的厚度為佳。保護鍍鎳層的厚度未滿0.1μm時，無法有效地防止包含於含有固體微粒子之電鍍鎳層的固體微粒子，在固體微粒子附著的線的操作時或切斷操作時發生脫落。另一方面，使保護鍍鎳厚的厚度，採用電鍍法作成超過40μm，則引起在鑽石粒子的頭頂部的電流集中，於該電流集中處發生鎳的異常析出，使鑽石粒子的頭頂部的鍍層變厚。此時假定使用於作為線鋸的固體微粒子附著的線，則鑽石粒子的頭頂部的鍍厚變較厚的狀態，則作為線鋸使用開始之後，由於鑽石的頭頂部不容易成為露出的狀態，而有降低初期切斷性能而不佳。 The protective nickel plating layer formed in this step d is provided on the outer surface of the electroplated nickel layer containing the solid fine particles, and is located at the outermost layer of the line to which the solid fine particles are attached. Therefore, by protecting the nickel plating layer, it is possible to effectively prevent the solid particles contained in the electroplated nickel layer containing the solid fine particles from falling off. The protective nickel plating layer preferably has a thickness of 0.1 to 40 μm. When the thickness of the protective nickel plating layer is less than 0.1 μm, the solid fine particles contained in the nickel plating layer containing the solid fine particles cannot be effectively prevented from falling off during the operation of the wire to which the solid fine particles adhere or during the cutting operation. On the other hand, when the thickness of the protective nickel plating is made to be more than 40 μm by electroplating, current concentration at the top of the diamond particles is caused, and abnormal precipitation of nickel occurs at the current concentration, so that the top of the diamond particles is plated. Thicken. At this time, it is assumed that the wire used for the attachment of the solid fine particles as the wire saw becomes thicker in the state of the top of the diamond particles, and since the use of the wire saw is started, the top of the diamond is not easily exposed. It is not good to reduce the initial cutting performance.
此外，使該保護鍍鎳層的厚度為2~4μm更佳。保護鍍鎳層，以0.1~40μm的厚度為佳。保護鍍鎳層的厚度為2μm，則可大致完全防止包含於含有固體微粒子之電鍍鎳層的固體微粒子在固體微粒子附著的線在操作時或切斷操作時發生脫落。然後，即使使保護鍍鎳層的厚度為超過4μm，防止包含於含有固體微粒子之電鍍鎳層的固體微粒子的脫落的效果已飽和，反而容易引起在鑽石粒子的頭頂部的電流集中，有使步驟管理繁瑣化的趨勢。 Further, it is more preferable that the protective nickel plating layer has a thickness of 2 to 4 μm. The nickel plating layer is preferably protected to a thickness of 0.1 to 40 μm. When the thickness of the protective nickel plating layer is 2 μm, the solid microparticles contained in the electroplated nickel layer containing the solid fine particles can be almost completely prevented from falling off during the operation or the cutting operation. Then, even if the thickness of the protective nickel plating layer is more than 4 μm, the effect of preventing the detachment of the solid fine particles contained in the electroplated nickel layer containing the solid fine particles is saturated, and conversely, current concentration at the top of the diamond particles is likely to occur, and the steps are made. Management is cumbersome.
在此，敘述關於該保護鍍鎳層的厚度的測定方法。將固體微粒子附著的線1的剖面，以金屬顯微鏡直接觀察，則如圖1所示意表示，可明顯地觀察，線2、無機保護層(衝擊鍍層)3，固體微粒子4、保護鍍鎳層5。此時，在保護鍍鎳層5的不存在固體微粒子4的地方測定保護鍍鎳層5的厚度。 Here, a method of measuring the thickness of the protective nickel plating layer will be described. The cross section of the line 1 to which the solid fine particles are attached is directly observed by a metal microscope, and is schematically shown in Fig. 1. It can be clearly observed, the line 2, the inorganic protective layer (impact plating layer) 3, the solid fine particles 4, and the protective nickel plating layer 5 . At this time, the thickness of the protective nickel plating layer 5 was measured at a place where the solid fine particles 4 were not protected in the nickel plating layer 5.
以下，表示實施例具體地說明本案發明。再者，本案發明並 不應解釋為限定於以下的實施例。 Hereinafter, the present invention will be specifically described with reference to examples. Furthermore, the invention of the case It should not be construed as being limited to the following examples.
[實施例1] [Example 1]
線：於實施例，使用直徑0.12mm的鋼線。先於後述的步驟c的含有固體微粒子之電鍍鎳層的形成，將線脫脂處理之後，施以浸漬10%硫酸之前處理。之後，對線的表面進行鎳衝擊鍍，設置厚度大約0.08μm的無機保護層。此時的鎳衝擊鍍，係使用氯化鎳240g/L、鹽酸125g/L之電解液，採用脈衝波形為方形波，頻率1000Hz，Duty Ratio(on：20、off：80)，電流密度6A/dm2~10A/dm2的脈衝電解條件。再者，在於其他的實施例及比較例亦使用同樣的線。 Line: In the examples, a steel wire having a diameter of 0.12 mm was used. The formation of the electroplated nickel layer containing the solid fine particles in the step c described later is carried out after the line is degreased, and then treated by impregnating 10% sulfuric acid. Thereafter, the surface of the wire was subjected to nickel impact plating to provide an inorganic protective layer having a thickness of about 0.08 μm. At this time, nickel impact plating is performed using an electrolyte of 240 g/L of nickel chloride and 125 g/L of hydrochloric acid, using a pulse wave as a square wave, a frequency of 1000 Hz, a Duty Ratio (on: 20, off: 80), and a current density of 6 A/ Pulse electrolysis conditions of dm 2 ~10A/dm 2 . Furthermore, the same lines are used in other embodiments and comparative examples.
固體微粒子：於實施例，使用平均粒徑為15μm的鑽石粒子作為固體微粒子。然後，使用該鑽石粒子，以如下方法製造固體微粒子附著的線。於後述的實施例2、實施例3及比較例亦使用同樣的鑽石粒子。 Solid fine particles: In the examples, diamond particles having an average particle diameter of 15 μm were used as solid fine particles. Then, using the diamond particles, a line to which solid fine particles adhered was produced in the following manner. The same diamond particles were also used in Example 2, Example 3, and Comparative Example described later.
步驟a：於實施例1，使用對鑽石粒子以鈀．錫膠體觸媒作為主要成分的溶液，使鈀與錫析出於鑽石粒子的表面的方法。於此實施例，溶液使用鈀濃度0.1g/l、錫濃度2g/l、40℃的溶液。將鑽石粒子浸漬於該溶液10分鐘之後，將鑽石粒子由溶液取出，水洗。之後，將鑽石粒子浸漬於濃度50g/l的硫酸10分鐘。藉此，於鑽石粒子的表面形成鈀塗層，得到「鈀塗層鑽石粒子」。 Step a: In Example 1, using palladium on diamond particles. A solution in which a tin colloid catalyst is used as a main component to precipitate palladium and tin on the surface of diamond particles. In this example, the solution used a solution having a palladium concentration of 0.1 g/l, a tin concentration of 2 g/l, and a temperature of 40 °C. After immersing the diamond particles in the 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. Thereby, a palladium coating layer is formed on the surface of the diamond particles to obtain "palladium-coated diamond particles".
步驟b：於此步驟，使用包含醇胺類的非離子系界面活性劑的溶液作為表面改質劑，進行「鈀塗層鑽石粒子」的粒子表面的表面改質處理。此時的表面改質劑，使用2-胺基乙醇(一級胺)1.0~30質量%、非離子系界面活性劑0.1~5.0質量%、pH9.0~12.5之溶液。然後，於表面改質處理，係將「鈀塗層鑽石粒子」放入液溫維持於大約30℃之該表面改質劑中，浸漬10分鐘之後，施以水洗。 Step b: In this step, a surface modification process of the surface of the "palladium-coated diamond particles" is performed using a solution containing a nonionic surfactant of an alcohol amine as a surface modifier. The surface modifier at this time is a solution of 1.0 to 30% by mass of 2-aminoethanol (primary amine), 0.1 to 5.0% by mass of a nonionic surfactant, and pH 9.0 to 12.5. Then, in the surface modification treatment, "palladium-coated diamond particles" were placed in the surface modifier having a liquid temperature maintained at about 30 ° C, and immersed for 10 minutes, and then washed with water.
步驟c：於此步驟，將結束步驟b之表面改質處理的鈀塗層鑽石粒子放入鎳電鍍液，得到鈀塗層鑽石粒子濃度為5g/L之懸浮狀態的「含有鑽石粒子之鎳電鍍液」。該含有鑽石粒子之鎳電鍍液，使用磺胺酸鎳．4水和物400g/L、氯化鎳．6水和物2g/L、硼酸35g/L、pH4.0的磺胺酸鎳鍍浴。 Step c: In this step, the palladium-coated diamond particles which have been subjected to the surface modification treatment of the step b are placed in a nickel plating solution to obtain a nickel plating plate containing diamond particles in a suspended state of a palladium-coated diamond particle concentration of 5 g/L. liquid". The nickel plating solution containing diamond particles uses nickel sulfamate. 4 water and 400g / L, nickel chloride. 6 water and material 2g / L, boric acid 35g / L, pH 4.0 nickel sulfate plating bath.
然後，使該含有鑽石粒子之鎳電鍍液的液溫為50℃，以電流密度15A/dm2電解，對上述脫脂處理的線的表面施以複合鍍，形成分散含 有鈀塗層鑽石粒子的「含有鑽石粒子之電鍍鎳層」。 Then, the liquid temperature of the nickel plating solution containing the diamond particles was 50 ° C, and electrolysis was performed at a current density of 15 A/dm 2 , and the surface of the degreased wire was subjected to composite plating to form a dispersion of the palladium-coated diamond particles. An electroplated nickel layer containing diamond particles."
步驟d：於該步驟，鍍液，使用磺胺酸鎳．4水和物450g/L、氯化鎳．6水和物3g/L、硼酸40g/L、pH4.0的磺胺酸鎳鍍浴。然後，將該鎳鍍液以液溫50℃，電流密度15A/dm2的條件，在步驟c設於線表面的含有鑽石粒子之電鍍鎳層的表面，形成厚度約4μm的「保護鍍鎳層」，而製造「鑽石微粒子附著的線」。 Step d: In this step, the plating solution, using nickel sulfamate. 4 water and matter 450g / L, nickel chloride. 6 water and material 3g / L, boric acid 40g / L, pH 4.0 nickel sulfate plating bath. Then, the nickel plating solution is placed on the surface of the electroplated nickel layer containing diamond particles on the surface of the wire at a liquid temperature of 50 ° C and a current density of 15 A/dm 2 to form a protective nickel plating layer having a thickness of about 4 μm. ", and the "line of diamond particles attached" is created.
於此實施例1製造的鑽石微粒子附著的線，係如圖2所示，對線的長度500μm，附著鈀塗層鑽石粒子約24個。此外，「保護鍍鎳層」的換算厚度為4.1μm。 The line to which the diamond fine particles produced in Example 1 adhered was as shown in Fig. 2, and the length of the line was 500 μm, and about 24 palladium-coated diamond particles were adhered. In addition, the "protective nickel plating layer" has a converted thickness of 4.1 μm.
[實施例2] [Embodiment 2]
於實施例2，只有步驟c之鈀塗層鑽石粒子的含量與實施例 1不同，其他的全部採用與實施例1相同的條件，製造鑽石微粒子附著的線。以下，僅說明關於與實施例1不同的步驟c的條件。 In Example 2, only the content of the palladium-coated diamond particles of the step c and the examples In the same manner as in Example 1, all of the other lines were used to produce a line in which diamond fine particles were attached. Hereinafter, only the conditions of the step c different from the first embodiment will be described.
於實施例2，在於步驟c，將懸浮於上述磺胺酸浴之鈀塗層鑽石粒子的濃度以10g/L，調製電鍍液。再者，其他的鍍液的溫度、電流密度等的條件與實施例1採用相同的條件。 In Example 2, in step c, the plating solution was prepared at a concentration of 10 g/L of the palladium-coated diamond particles suspended in the above sulfamic acid bath. Further, the conditions of the temperature, current density, and the like of the other plating solution were the same as those in the first embodiment.
於此實施例2所製造的鑽石微粒子附著的線，如圖3所示，對線的長度500μm，附著鈀塗層鑽石粒子約31個。此外，「保護鍍鎳層」的換算厚度為4.2μm。 As shown in Fig. 3, the wire to which the diamond fine particles produced in Example 2 adhered had a length of 500 μm for the wire and about 31 palladium-coated diamond particles. In addition, the "protective nickel plating layer" has a converted thickness of 4.2 μm.
[實施例3] [Example 3]
於實施例3，只有步驟c之鈀塗層鑽石粒子的含量與實施例1不同，其他的全部採用與實施例1相同的條件，製造鑽石微粒子附著的線。以下，僅說明關於與實施例1不同的步驟c的條件。 In Example 3, only the content of the palladium-coated diamond particles of the step c was different from that of the first embodiment, and all the other conditions were the same as those of the first embodiment, and the line to which the diamond fine particles were attached was produced. Hereinafter, only the conditions of the step c different from the first embodiment will be described.
於實施例3，在於步驟c，將懸浮於上述磺胺酸浴之鈀塗層鑽石粒子的濃度以15g/L，調製電鍍液。再者，其他的鍍液的溫度、電流密度等的條件與實施例1採用相同的條件。 In Example 3, in step c, the plating solution was prepared at a concentration of 15 g/L of the palladium-coated diamond particles suspended in the above sulfamic acid bath. Further, the conditions of the temperature, current density, and the like of the other plating solution were the same as those in the first embodiment.
於此實施例3所製造的鑽石微粒子附著的線，如圖4所示，對線的長度500μm，附著鈀塗層鑽石粒子約46個。此外，「保護鍍鎳層」的換算厚度為4.3μm。 As shown in Fig. 4, the wire to which the diamond fine particles produced in Example 3 adhered had a length of 500 μm for the wire and about 46 palladium-coated diamond particles. In addition, the "protective nickel plating layer" has a converted thickness of 4.3 μm.
[實施例4] [Example 4]
於實施例4，取代實施例1的步驟a所調製的鈀塗層鑽石粒子而使用市售的同一粒徑的鎳過鑽石粒子。 In Example 4, a commercially available nickel over diamond particle of the same particle diameter was used instead of the palladium-coated diamond particles prepared in the step a of Example 1.
然後，採用與實施例2的步驟c的鑽石粒子的含量相同的含量。即，於實施例4的步驟c，只有「將結束步驟b之表面改質處理的鎳塗層鑽石粒子放入鎳電鍍液，得到鈀塗層鑽石粒子濃度為10g/L之懸浮狀態的含有鑽石粒子之鎳電鍍液。」的點與實施例1不同，其他的全部採用與實施例1相同的條件，製造鎳過鑽石粒子附著的線。 Then, the same content as that of the diamond particles of the step c of Example 2 was employed. That is, in the step c of the fourth embodiment, only the nickel-coated diamond particles which have been subjected to the surface modification treatment of the step b are placed in a nickel plating solution to obtain a diamond containing a palladium-coated diamond particle concentration of 10 g/L. The nickel plating solution of particles was different from that of Example 1, and all the other conditions were the same as in Example 1, and a line in which nickel over diamond particles adhered was produced.
於此實施例4所製造的鑽石微粒子附著的線，如圖5所示，對線的長度500μm，附著鈀塗層鑽石粒子約30個。此外，「保護鍍鎳層」的換算厚度為4.1μm。 As shown in Fig. 5, the wire to which the diamond fine particles produced in Example 4 adhered had a length of 500 μm for the wire and about 30 palladium-coated diamond particles. In addition, the "protective nickel plating layer" has a converted thickness of 4.1 μm.
[實施例5] [Example 5]
於此實施例4，取代實施例1的步驟a所調製的鈀塗層鑽石粒子而使用市售的同一粒徑的鎳過鑽石粒子。 In Example 4, a commercially available nickel over diamond particle of the same particle diameter was used instead of the palladium-coated diamond particles prepared in the step a of Example 1.
然後，採用與實施例2的步驟c的鑽石粒子的含量相同的含量。即，於實施例4的步驟c，只有「將結束步驟b之表面改質處理的鈦塗層鑽石粒子放入鎳電鍍液，得到鈀塗層鑽石粒子濃度為10g/L之懸浮狀態的含有鑽石粒子之鎳電鍍液。」的點與實施例1不同，其他的全部採用與實施例1相同的條件，製造鎳過鑽石粒子附著的線。 Then, the same content as that of the diamond particles of the step c of Example 2 was employed. That is, in the step c of the fourth embodiment, only the titanium-coated diamond particles which have been subjected to the surface modification treatment of the step b are placed in the nickel plating solution to obtain a diamond containing a palladium-coated diamond particle concentration of 10 g/L. The nickel plating solution of particles was different from that of Example 1, and all the other conditions were the same as in Example 1, and a line in which nickel over diamond particles adhered was produced.
於此實施例4所製造的鑽石微粒子附著的線，如圖6所示，對線的長度500μm，附著鈀塗層鑽石粒子約32個。此外，「保護鍍鎳層」的換算厚度為4.2μm。 As shown in Fig. 6, the line to which the diamond fine particles produced in Example 4 adhered had a length of 500 μm for the line and about 32 palladium-coated diamond particles. In addition, the "protective nickel plating layer" has a converted thickness of 4.2 μm.
[比較例1] [Comparative Example 1]
此比較例1，係對實施例1的步驟a所得的鈀塗層鑽石粒子不進行步驟b之表面改質處理，施以步驟c之鍍敷製造固體微粒子附著的線。藉此，驗証不進行步驟b的表面改質處理時的線的鑽石粒子的附著量。 In Comparative Example 1, the palladium-coated diamond particles obtained in the step a of Example 1 were subjected to the surface modification treatment of the step b, and the plating of the step c was applied to produce a line in which the solid particles adhered. Thereby, the amount of adhesion of the diamond particles of the wire when the surface modification treatment of the step b was not performed was verified.
於比較例1，不進行實施例1的步驟b，以表面改質劑的表面改質處理步驟，對實施例1的步驟a所得的鈀塗層鑽石粒子，以實施例1的步驟c所述的磺胺酸浴以5g/L的濃度濁浮調製鍍液。再者，比較例1，只有不進行步驟b之點與實施例1不同，其他的步驟，使用的鑽石粒子、線、鍍條件等均採用與上述實施例相同條件。 In Comparative Example 1, the palladium-coated diamond particles obtained in the step a of Example 1 were subjected to the surface modification treatment step of the surface modifier without performing the step b of Example 1, as described in the step c of Example 1. The sulfamic acid bath was turbidly floated at a concentration of 5 g/L. Further, in Comparative Example 1, only the point where the step b was not performed was different from that of the first embodiment, and the other steps, the diamond particles, the wire, the plating conditions, and the like used were the same as those of the above examples.
於此比較例1所製造的鑽石微粒子附著的線，如圖7所示，對線的長度500μm，附著鈀塗層鑽石粒子約8個。此外，「保護鍍鎳層」的換算厚度為4.1μm。 As shown in Fig. 7, the line to which the diamond fine particles produced in Comparative Example 1 adhered had a length of 500 μm for the line and about 8 palladium-coated diamond particles. In addition, the "protective nickel plating layer" has a converted thickness of 4.1 μm.
[比較例2] [Comparative Example 2]
於比較例2，係對實施例1的步驟a所得的鈀塗層鑽石粒子不進行步驟b之表面改質處理，施以步驟c之鍍敷製造固體微粒子附著的線。藉此，驗証不進行步驟b的表面改質處理時的線的鑽石粒子的附著量。 In Comparative Example 2, the palladium-coated diamond particles obtained in the step a of Example 1 were subjected to the surface modification treatment of the step b, and the plating of the step c was applied to produce a line in which the solid particles adhered. Thereby, the amount of adhesion of the diamond particles of the wire when the surface modification treatment of the step b was not performed was verified.
於比較例1，不進行實施例1的步驟b，以表面改質劑的表面改質處理步驟，對實施例1的步驟a所得的鈀塗層鑽石粒子，以實施例1的步驟c所述的磺胺酸浴以10g/L的濃度濁浮調製鍍液。再者，比較例1，只有不進行步驟b之點與實施例1不同，其他的步驟，使用的鑽石粒子、線、鍍條件等均採用與上述實施例相同條件。 In Comparative Example 1, the palladium-coated diamond particles obtained in the step a of Example 1 were subjected to the surface modification treatment step of the surface modifier without performing the step b of Example 1, as described in the step c of Example 1. The sulfanilic acid bath was turbidly floated at a concentration of 10 g/L. Further, in Comparative Example 1, only the point where the step b was not performed was different from that of the first embodiment, and the other steps, the diamond particles, the wire, the plating conditions, and the like used were the same as those of the above examples.
於此比較例2所製造的鑽石微粒子附著的線，係與圖7同樣的形態，對線的長度500μm，附著鈀塗層鑽石粒子約8個。此外，「保護鍍鎳層」的換算厚度為4.0μm。 The line to which the diamond fine particles produced in Comparative Example 2 adhered was in the same manner as in Fig. 7, and the length of the wire was 500 μm, and about 8 palladium-coated diamond particles were adhered. Further, the "protective nickel plating layer" has a converted thickness of 4.0 μm.
[比較例3] [Comparative Example 3]
此比較例3，係對實施例1的步驟a所得的鈀塗層鑽石粒子不進行步驟b之表面改質處理，施以步驟c之鍍敷製造固體微粒子附著的線。藉此，驗証不進行步驟b的表面改質處理時的線的鑽石粒子的附著量。 In Comparative Example 3, the palladium-coated diamond particles obtained in the step a of Example 1 were subjected to the surface modification treatment of the step b, and the plating of the step c was applied to produce a line in which the solid particles adhered. Thereby, the amount of adhesion of the diamond particles of the wire when the surface modification treatment of the step b was not performed was verified.
於比較例1，不進行實施例1的步驟b，以表面改質劑的表面改質處理步驟，對實施例1的步驟a所得的鈀塗層鑽石粒子，以實施例1的步驟c所述的磺胺酸浴以15g/L的濃度濁浮調製鍍液。再者，比較例1，只有不進行步驟b之點與實施例1不同，其他的步驟，使用的鑽石粒子、線、鍍條件等均採用與上述實施例相同條件。 In Comparative Example 1, the palladium-coated diamond particles obtained in the step a of Example 1 were subjected to the surface modification treatment step of the surface modifier without performing the step b of Example 1, as described in the step c of Example 1. The sulfamic acid bath was turbidly floated at a concentration of 15 g/L. Further, in Comparative Example 1, only the point where the step b was not performed was different from that of the first embodiment, and the other steps, the diamond particles, the wire, the plating conditions, and the like used were the same as those of the above examples.
於此比較例2所製造的鑽石微粒子附著的線，係與圖7同樣的形態，對線的長度500μm，附著鈀塗層鑽石粒子約9個。此外，「保護鍍鎳層」的換算厚度為4.1μm。 The line to which the diamond fine particles produced in Comparative Example 2 adhered was in the same manner as in Fig. 7, and the length of the wire was 500 μm, and about nine palladium-coated diamond particles were adhered. In addition, the "protective nickel plating layer" has a converted thickness of 4.1 μm.
[由實施例與比較例的對比的討論] [Discussion of comparison between embodiment and comparative example]
可容易地將實施例與比較例對比地，於以下的表1，表示所製造的鑽石微粒子附著的線的觀察結果。 The observation results of the line to which the produced diamond fine particles were attached can be easily observed in the following Table 1 in comparison with the comparative examples.
關於有無表面改質處理，參照表1說明。首先，敘述關於可由實施例瞭解之事。實施例1~實施例3，係改變包含於步驟c的鎳電鍍液的鑽石粒子的含量者。由該實施例1~實施例3，可知的是，將包含於鎳電鍍液的鑽石粒子的含量，由5g/l→10g/l→15g/l變化，則附著在鑽石微粒子附著的線的鑽石粒子的個數，由24個→31個→46個，隨著鎳電鍍液所含有的鑽石粒子的含量的增加，而附著在鑽石微粒子附著的線的鑽石微粒子個數亦明顯地成比例增加。 The presence or absence of surface modification treatment will be described with reference to Table 1. First, the description of what can be understood by the embodiment is described. Examples 1 to 3 are those in which the content of the diamond particles contained in the nickel plating solution of the step c is changed. According to the first to third embodiments, it is understood that the diamond particles contained in the nickel plating solution are changed from 5 g/l to 10 g/l to 15 g/l, and the diamond adheres to the line to which the diamond particles adhere. The number of particles is from 24 to 31 → 46. As the content of diamond particles contained in the nickel plating solution increases, the number of diamond particles adhering to the line to which the diamond particles adhere is also significantly increased proportionally.
在此，看比較例1~比較例3，則該等的比較例，亦係將包含於鎳電鍍液的鑽石粒子的含量，由5g/l→10g/l→15g/l變化，但是附著在鑽石微粒子附著的線的鑽石粒子的個數，則為8個~9個，可知鑽石粒子的附著量的變化很少。即，在於比較例，即使增加包含於鎳電鍍液的鑽石粒子的含量，附著在鑽石微粒子附著的線的鑽石微粒子的個數，並不會成增加。而且，包含於鎳電鍍液的鑽石粒子的含量相同時，比對實施例與比較例，可容易地理解實施例的附著個數明顯較多。 Here, in Comparative Example 1 to Comparative Example 3, the comparative examples also change the content of the diamond particles contained in the nickel plating solution from 5 g/l to 10 g/l to 15 g/l, but adhered thereto. The number of diamond particles in the line to which the diamond particles adhere is 8 to 9, and it is known that the amount of adhesion of the diamond particles is small. That is, in the comparative example, even if the content of the diamond particles contained in the nickel plating solution is increased, the number of the diamond fine particles adhering to the line to which the diamond fine particles adhere is not increased. Further, when the content of the diamond particles contained in the nickel plating solution was the same, it was easy to understand that the number of adhesions in the examples was significantly higher than in the examples and the comparative examples.
由以上可知，在於鑽石微粒子附著的線之製造，藉由使用含有醇胺類的非離子系界面活性劑的溶液作為表面改質劑，進行該鈀塗層鑽 石粒子的粒子表面的表面改質處理，可於鑽石微粒子附著的線的表面，均勻且確實地使鑽石粒子附著，亦可控制附著的鑽石粒子量。 From the above, it is understood that the palladium coating is drilled by using a solution containing a nonionic surfactant containing an alcohol amine as a surface modifier in the production of a line to which fine particles of diamond are attached. The surface modification treatment of the particle surface of the stone particles can uniformly and surely adhere the diamond particles to the surface of the line to which the diamond particles adhere, and can also control the amount of the adhered diamond particles.
關於以上所敘述的實施例之固體微粒子附著的線，與比較例的固體微粒子附著的線，作成線鋸使用，則可知實施例的固體微粒子附著的線相較於比較例的固體微粒子附著的線，切斷性能飛躍地提高，且可長時間使用。 When the line to which the solid fine particles adhered to the above-described examples were attached to the solid fine particles of the comparative example and used as a wire saw, it was found that the line to which the solid fine particles of the example adhered was compared with the line to which the solid fine particles of the comparative example adhered. The cutting performance is greatly improved and can be used for a long time.
[產業上的利用可能性] [Industry use possibility]
如以上所述，採用關於本案發明之製造方法所得之固體微粒子附著的線，可顯著地提高附著在線的固體微粒子的附著量，且可有效地抑制附著的固體微粒子的脫落。藉此，可以低成本提供作為線鋸的切斷性能優良，可長期使用的固體微粒子附著的線。所關固體微粒子附著的線，由於可以高精度地進行單結晶矽的晶柱等的高脆性材料的切斷作業，故可良好地使用於太陽能電池或半導體用矽晶圓等的製造步驟。此外，由於關於本案發明之固體微粒子附著的線的優良的研磨性能，亦可適用於銼刀、或磨刀等的各種用途，需要切斷或研削之各式各樣的用途。 As described above, by using the wire attached to the solid fine particles obtained by the production method of the present invention, the amount of adhesion of the solid fine particles adhering to the wire can be remarkably improved, and the fall of the adhered solid fine particles can be effectively suppressed. Thereby, it is possible to provide a wire which is excellent in the cutting performance of the wire saw and which can be used for long-term use of solid fine particles. Since the line to which the solid fine particles are attached can be cut with a high-brittle material such as a crystal column of a single crystal ruthenium with high precision, it can be suitably used in a manufacturing process of a solar cell or a germanium wafer for semiconductor. Further, the excellent polishing performance of the wire to which the solid fine particles adhered in the present invention can be applied to various applications such as a file or a sharpening blade, and various applications such as cutting or grinding are required.
1‧‧‧固體微粒子附著的線符號 1‧‧‧Line symbol attached to solid particles
2‧‧‧線 2‧‧‧ line
3‧‧‧無機保護層(衝擊鍍層) 3‧‧‧Inorganic protective layer (impact coating)
4‧‧‧固體微粒子 4‧‧‧Solid microparticles
5‧‧‧保護鍍鎳層 5‧‧‧Protective nickel plating
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| CN106414807A (en) * | 2015-05-29 | 2017-02-15 | Facility有限公司 | Nickel plating liquid, method for manufacturing wire coated with solid microparticles, and wire coated with solid microparticles |
| CN108286066A (en) * | 2018-02-07 | 2018-07-17 | 浙江新瑞欣精密线锯有限公司 | A kind of diamond cutting secant processing method and device |
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| JP5705813B2 (en) * | 2011-12-02 | 2015-04-22 | 古河電気工業株式会社 | Diamond abrasive manufacturing method, wire tool manufacturing method, and wire tool |
| FR3005592B1 (en) * | 2013-05-14 | 2015-04-24 | Commissariat Energie Atomique | ABRASIVE SAWING WIRE |
| JP6119495B2 (en) * | 2013-08-05 | 2017-04-26 | 新日鐵住金株式会社 | Saw wire and core wire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4157724B2 (en) * | 2002-05-20 | 2008-10-01 | 株式会社ノリタケカンパニーリミテド | Wire saw manufacturing method and manufacturing apparatus |
| JP4139810B2 (en) * | 2004-12-28 | 2008-08-27 | 旭ダイヤモンド工業株式会社 | Electrodeposition wire tool |
| TW200948565A (en) * | 2008-04-11 | 2009-12-01 | Almt Corp | Electrodeposited wire tool and method of producing same |
| JP5356071B2 (en) * | 2009-03-02 | 2013-12-04 | 住友電気工業株式会社 | Diamond wire saw, diamond wire saw manufacturing method |
| CN102574275A (en) * | 2009-10-06 | 2012-07-11 | 日本精细钢铁株式会社 | Fixed abrasive grain wire, process for producing the fixed abrasive grain wire, and abrasive grains for use in fixed abrasive grain wire |
| JP5522604B2 (en) * | 2009-12-09 | 2014-06-18 | 日本精線株式会社 | Wire tool |
| CN101812710A (en) * | 2010-04-26 | 2010-08-25 | 长沙岱勒金刚石制品有限公司 | Diamond wire saw production method of surface modified diamond |
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| CN106414807A (en) * | 2015-05-29 | 2017-02-15 | Facility有限公司 | Nickel plating liquid, method for manufacturing wire coated with solid microparticles, and wire coated with solid microparticles |
| CN106414807B (en) * | 2015-05-29 | 2018-07-27 | Facility有限公司 | Nickel-plating liquid, the manufacturing method of solia particle adhesion metal line and solia particle adhesion metal line |
| TWI637085B (en) * | 2015-05-29 | 2018-10-01 | 法西利迪股份有限公司 | Manufacturing method of nickel plating solution and steel wire with solid particles attached |
| CN108286066A (en) * | 2018-02-07 | 2018-07-17 | 浙江新瑞欣精密线锯有限公司 | A kind of diamond cutting secant processing method and device |
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| TWI551732B (en) | 2016-10-01 |
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