TWI519366B - Resin fixed wire saws - Google Patents

Resin fixed wire saws Download PDF

Info

Publication number
TWI519366B
TWI519366B TW102146989A TW102146989A TWI519366B TW I519366 B TWI519366 B TW I519366B TW 102146989 A TW102146989 A TW 102146989A TW 102146989 A TW102146989 A TW 102146989A TW I519366 B TWI519366 B TW I519366B
Authority
TW
Taiwan
Prior art keywords
resin
weight
parts
wire
wire saw
Prior art date
Application number
TW102146989A
Other languages
Chinese (zh)
Other versions
TW201433391A (en
Inventor
Masahiko Ikeuchi
Tadashi Endo
Original Assignee
Tkx Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tkx Corp filed Critical Tkx Corp
Publication of TW201433391A publication Critical patent/TW201433391A/en
Application granted granted Critical
Publication of TWI519366B publication Critical patent/TWI519366B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B27/00—Other grinding machines or devices
    • B24B27/06—Grinders for cutting-off
    • B24B27/0633—Grinders for cutting-off using a cutting wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D61/00—Tools for sawing machines or sawing devices; Clamping devices for these tools
    • B23D61/18—Sawing tools of special type, e.g. wire saw strands, saw blades or saw wire equipped with diamonds or other abrasive particles in selected individual positions
    • B23D61/185—Saw wires; Saw cables; Twisted saw strips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B24D3/20—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 organic
    • B24D3/28—Resins or natural or synthetic macromolecular compounds

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Rotary Pumps (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Description

樹脂固定線鋸 Resin fixed wire saw

本發明係關於一種用於矽晶錠等之切斷之樹脂固定線鋸(resin bond wire saw)。樹脂固定線鋸係藉由樹脂黏合劑(樹脂接著劑)將研磨粒固定於線上者。用於切斷之線亦被稱為「鋸條」，於本申請案說明書中稱為「線鋸」。 The present invention relates to a resin bond wire saw for cutting a twin ingot or the like. The resin-fixed wire saw is a method in which the abrasive grains are fixed to the wire by a resin binder (resin adhesive). The line for cutting is also referred to as a "saw blade" and is referred to as a "wire saw" in the specification of the present application.

先前，矽晶錠之切斷一直使用內周刀切塊機。然而，隨著矽晶錠之大型化，內周刀切塊機產生生產性降低、產生加工變質層、尺寸精度降低、裝置大型化等問題。因此，近年來逐漸實施使用線鋸之切斷。使用線鋸之切斷易於應對錠之大型化。又，以1次切斷即可獲得複數片晶圓。 Previously, the cutting of the ingot was always using an inner peripheral knife cutting machine. However, with the increase in the size of the twin ingots, the inner peripheral knife cutting machine has problems such as reduced productivity, generation of a deteriorated layer, reduction in dimensional accuracy, and enlargement of the apparatus. Therefore, the cutting using a wire saw has been gradually implemented in recent years. It is easy to deal with the enlargement of the ingot by cutting with a wire saw. Further, a plurality of wafers can be obtained by cutting once.

線鋸存在游離研磨粒線鋸與固定研磨粒線鋸。游離研磨粒線鋸使用鋼琴線等線、及使研磨粒分散於液體中而成之研磨粒液。研磨粒為金剛石微粒或碳化矽微粒等。游離研磨粒線鋸係一面將研磨粒液滴加至切斷部，一面使線移行而實施切斷(專利文獻1：日本專利特開2008-103690)。游離研磨粒線鋸係藉由夾於線與錠之間之研磨粒而將錠切斷。 The wire saw has a free abrasive wire saw and a fixed abrasive wire saw. The free abrasive granule saw uses a piano thread and the like, and an abrasive granule obtained by dispersing abrasive grains in a liquid. The abrasive grains are diamond fine particles or cerium carbide fine particles. In the case of the free-abrasive granule saw, the abrasive granules are applied to the cut portion, and the wire is moved to perform cutting (Patent Document 1: JP-A-2008-103690). The free abrasive grain saw is cut by the abrasive grains sandwiched between the wire and the ingot.

游離研磨粒線鋸中，由於研磨粒液之黏度隨溫度而變動，故而晶圓之厚度不均，或者晶圓之平面性變差。又，游離研磨粒線鋸之線亦因研磨粒而磨損，因此難以使用較細之線。進而，游離研磨粒線鋸有於晶圓表面形成較厚之加工變質層之虞。 In the free abrasive granule saw, since the viscosity of the abrasive granules fluctuates with temperature, the thickness of the wafer is uneven, or the planarity of the wafer is deteriorated. Moreover, the line of the free abrasive granule saw is also worn by the abrasive grains, so that it is difficult to use a thinner wire. Further, the free abrasive grain saw has a thicker textured layer on the surface of the wafer.

為了解決游離研磨粒線鋸之問題，業界提出有將研磨粒固定於線表面之固定研磨粒線鋸。作為將研磨粒固定於線表面之方法，有電鍍法、焊接法、樹脂黏合法。 In order to solve the problem of free abrasive wire saws, the industry has proposed a fixed abrasive wire saw for fixing abrasive grains to the surface of the wire. As a method of fixing the abrasive grains to the surface of the wire, there are an electroplating method, a welding method, and a resin bonding method.

電鍍法係藉由鍍鎳等而將研磨粒固定於線表面(專利文獻2：日本專利特公平4-4105、專利文獻3：日本專利特開2003-334763)。電鍍法中，一面於鍍鎳液中使鎳於線表面析出一面將研磨粒埋設於鎳膜中。電鍍法由於研磨粒之固定較為牢固，故而錠之切斷性能優異。 In the electroplating method, the abrasive grains are fixed to the surface of the wire by nickel plating or the like (Patent Document 2: Japanese Patent Laid-Open No. Hei-4-4105, Patent Document 3: Japanese Patent Laid-Open No. 2003-334763). In the electroplating method, the abrasive grains are buried in the nickel film while depositing nickel on the surface of the wire in the nickel plating solution. Since the plating method is relatively strong in fixing the abrasive grains, the ingot has excellent cutting performance.

電鍍法中，將研磨粒深埋於電鍍層中而固定。由於必需較厚之電鍍皮膜，故而電鍍法之生產性變差，成本增大。進而，線因鍍鎳層而變粗，因此線容易產生疲勞斷裂。 In the electroplating method, the abrasive grains are deeply buried in the plating layer and fixed. Since a thick plating film is required, the productivity of the plating method is deteriorated and the cost is increased. Further, since the wire is thickened by the nickel plating layer, the wire is liable to cause fatigue fracture.

焊接法中，於線表面形成釺料層，並將研磨粒埋入至熔融之釺料層中，使釺料層凝固而將研磨粒固定(專利文獻4：日本專利特開2006-123024)。於釺料之熔點較高之情形時，釺料層熔融時線被過度加熱，導致線之強度降低。因此，焊接法中線材之選擇較難。難以使用於較低溫度下強度降低之鋼琴線或硬鋼線，而使用不鏽鋼線或鎢線。反之於釺料之熔點較低之情形時，有釺料因錠之切斷時之摩擦熱而熔融，導致研磨粒脫落之虞。 In the welding method, a crucible layer is formed on the surface of the wire, and the abrasive grains are buried in the molten crucible layer to solidify the crucible layer to fix the abrasive grains (Patent Document 4: Japanese Patent Laid-Open No. 2006-123024). In the case where the melting point of the crucible is high, the strand is excessively heated when it is melted, resulting in a decrease in the strength of the strand. Therefore, the selection of the wire in the welding method is difficult. It is difficult to use a piano wire or a hard steel wire with a reduced strength at a lower temperature, and a stainless steel wire or a tungsten wire is used. On the other hand, when the melting point of the dip is low, the crucible melts due to the frictional heat when the ingot is cut, and the abrasive grains fall off.

樹脂黏合法中，將液狀之樹脂黏合劑(樹脂接著劑)與研磨粒之混合物塗佈於線表面，並利用燒附爐加熱(專利文獻4：日本專利特開2006-123024)。利用藉由加熱而硬化之樹脂黏合劑而將研磨粒固定(專利文獻5：日本專利特開2000-263452、專利文獻6：日本專利特開2000-271872、專利文獻7：日本再公表專利WO98/35784)。作為燒附爐，已知有熱風乾燥爐(專利文獻8：日本專利特開平09-35556、專利文獻9：日本專利特開2010-267533)。 In the resin adhesive method, a mixture of a liquid resin adhesive (resin adhesive) and abrasive grains is applied to the surface of the wire and heated by a firing furnace (Patent Document 4: Japanese Patent Laid-Open No. 2006-123024). The abrasive grain is fixed by a resin adhesive which is hardened by heating (Patent Document 5: Japanese Patent Laid-Open No. 2000-263452, Patent Document 6: Japanese Patent Laid-Open No. 2000-271872, Patent Document 7: Japanese Re-Patent Patent WO98/ 35784). A hot air drying furnace is known as a baking furnace (Patent Document 8: Japanese Patent Laid-Open No. Hei 09-35556, Patent Document No. 9: Japanese Patent Laid-Open No. 2010-267533).

樹脂黏合法適合於製作廉價且長條之線鋸。進而，由於錠之切斷過程中產生之線鋸之振動經柔軟之樹脂黏合劑吸收，故而可使線鋸 高速地穩定移行。又，可獲得較薄之晶圓。另一方面，由於樹脂固定線鋸之研磨粒之保持力較低，故而於切斷過程中研磨粒容易脫落。於使用熱硬化型樹脂黏合劑之情形時，由於樹脂黏合劑之硬化需要較長時間，故而線鋸之製造會花費時間。此外，若於高溫下進行樹脂黏合劑之硬化，則因揮發成分而產生氣泡。 Resin bonding is suitable for making inexpensive and long wire saws. Further, since the vibration of the wire saw generated during the cutting process of the ingot is absorbed by the soft resin adhesive, the wire saw can be made Stable travel at high speed. Also, a thinner wafer can be obtained. On the other hand, since the holding force of the abrasive grains of the resin-fixed wire saw is low, the abrasive grains are easily peeled off during the cutting process. In the case of using a thermosetting resin adhesive, since the curing of the resin adhesive takes a long time, the manufacture of the wire saw takes time. Further, when the resin binder is cured at a high temperature, bubbles are generated due to the volatile component.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2008-103690號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-103690

[專利文獻2]日本專利特公平4-4105號公報 [Patent Document 2] Japanese Patent Special Fair No. 4-4105

[專利文獻3]日本專利特開2003-334763號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-334763

[專利文獻4]日本專利特開2006-123024號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2006-123024

[專利文獻5]日本專利特開2000-263452號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-263452

[專利文獻6]日本專利特開2000-271872號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-271872

[專利文獻7]日本再公表專利WO98/35784號公報 [Patent Document 7] Japanese Re-publication Patent WO98/35784

[專利文獻8]日本專利特開平09-35556號公報 [Patent Document 8] Japanese Patent Laid-Open No. 09-35556

[專利文獻9]日本專利特開2010-267533號公報 [Patent Document 9] Japanese Patent Laid-Open Publication No. 2010-267533

本發明之目的在於提供一種切斷性能良好且壽命較長之樹脂固定線鋸。 It is an object of the present invention to provide a resin-fixed wire saw having good cutting performance and long life.

本發明者等人發現，藉由如下方法可達成本發明之目的：(1)使用含有酚醛清漆型(novolak type)酚系樹脂與可溶酚醛型(resol type)酚系樹脂以及胺系矽烷偶合劑之樹脂作為樹脂黏合劑，(2)藉由紅外線照射使樹脂黏合劑硬化。藉由本發明，可高效率地製造切斷性能優異且研磨粒較少脫落之壽命較長之樹脂固定線鋸。 The inventors of the present invention have found that the object of the invention can be achieved by the following methods: (1) using a novolak type phenolic resin and a resol type phenolic resin and an amine decane couple The resin of the mixture is used as a resin binder, and (2) the resin binder is cured by infrared irradiation. According to the present invention, it is possible to efficiently produce a resin-fixed wire saw having a long life with excellent cutting performance and less abrasive particles falling off.

本發明之樹脂固定線鋸係藉由以酚系樹脂為主成分之樹脂黏合劑而將研磨粒固定於線之表面。本發明所使用之樹脂黏合劑藉由利用MALDI-TOF-MS法進行之質量分析而於陽離子中檢測出顯示208(m/z)間隔之片段之波峰。又，藉由熱重-示差熱分析(TG-DTA)法於175℃~182℃檢測出相當於軟化點之波峰。(MALDI(Matrix Assisted Laser Desorption Ionization)：基質輔助雷射脫附游離法，TOF-MS(Time of Flight-Mass Spectrometry)：飛行時間型質譜法)。 In the resin-fixed wire saw of the present invention, the abrasive grains are fixed to the surface of the wire by a resin binder containing a phenol resin as a main component. The resin binder used in the present invention detects a peak showing a fragment of 208 (m/z) interval in the cation by mass analysis by the MALDI-TOF-MS method. Further, a peak corresponding to the softening point was detected by a thermogravimetry-differential thermal analysis (TG-DTA) method at 175 ° C to 182 ° C. (MALDI (Matrix Assisted Laser Desorption Ionization): TOF-MS (Time of Flight-Mass Spectrometry): time-of-flight mass spectrometry).

本發明所使用之樹脂黏合劑含有酚醛清漆型酚系樹脂：100重量份、可溶酚醛型酚系樹脂：10重量份~30重量份、胺系矽烷偶合劑：0.1重量份~5重量份。 The resin binder used in the present invention contains a novolac type phenol resin: 100 parts by weight, a novolac type phenol resin: 10 parts by weight to 30 parts by weight, and an amine decane coupling agent: 0.1 parts by weight to 5 parts by weight.

藉由本發明，而實現切斷性能良好且壽命較長之樹脂固定線鋸。 According to the present invention, a resin-fixed wire saw having good cutting performance and long life can be realized.

2‧‧‧凹面鏡 2‧‧‧ concave mirror

3‧‧‧線 3‧‧‧ line

4‧‧‧紅外線加熱器 4‧‧‧Infrared heater

6‧‧‧聚光部 6‧‧‧Concentration Department

8‧‧‧反射面 8‧‧‧reflecting surface

圖1係對塗佈於線上之糊劑進行紅外線加熱之方法的說明圖。 Fig. 1 is an explanatory view showing a method of infrared heating of a paste applied to a wire.

圖2係燈之能量分光分佈。 Figure 2 is an energy splitting distribution of a lamp.

圖3係利用MALDI-TOF-MS法進行之質量分析之陽離子測定圖表(比較例)。 Fig. 3 is a cation measurement chart (comparative example) of mass analysis by the MALDI-TOF-MS method.

圖4係利用MALDI-TOF-MS法進行之質量分析之陽離子測定圖表(實施例1)。 Fig. 4 is a cation measurement chart (Example 1) for mass analysis by the MALDI-TOF-MS method.

圖5係利用MALDI-TOF-MS法進行之質量分析之陰離子測定圖表(比較例)。 Fig. 5 is an anion measurement chart (comparative example) for mass analysis by the MALDI-TOF-MS method.

圖6係利用MALDI-TOF-MS法進行之質量分析之陰離子測定圖表(實施例1)。 Fig. 6 is an anion measurement chart (Example 1) for mass analysis by the MALDI-TOF-MS method.

圖7係實施例1及比較例之示差熱分析圖表。 Fig. 7 is a differential thermal analysis chart of Example 1 and Comparative Example.

本發明之樹脂固定線鋸係藉由含有酚醛清漆型酚系樹脂與可溶酚醛型酚系樹脂以及胺系矽烷偶合劑之樹脂黏合劑而將研磨粒固定於線表面。 In the resin-fixed wire saw of the present invention, the abrasive grains are fixed to the surface of the wire by a resin binder containing a novolac type phenol resin, a novolac type phenol resin, and an amine-based decane coupling agent.

酚醛清漆型酚系樹脂係使苯酚、甲酚、雙酚A等酚化合物與甲醛等醛於酸性觸媒下進行縮合反應而成者。可溶酚醛型酚系樹脂係使苯酚、甲酚、雙酚A等酚化合物與甲醛等醛於鹼性觸媒下進行縮合反應而成者。 The novolac type phenol-based resin is obtained by subjecting a phenol compound such as phenol, cresol or bisphenol A to an aldehyde such as formaldehyde to undergo condensation reaction under an acidic catalyst. The resol type phenol-based resin is obtained by subjecting a phenol compound such as phenol, cresol or bisphenol A to an aldehyde such as formaldehyde under a basic catalyst.

樹脂黏合劑亦可進而含有硬化劑。硬化劑較佳為相對於酚醛清漆型酚系樹脂100重量份，含有5重量份~20重量份。 The resin binder may further contain a hardener. The curing agent is preferably contained in an amount of from 5 parts by weight to 20 parts by weight per 100 parts by weight of the novolac type phenol resin.

若硬化劑相對於酚醛清漆型酚系樹脂100重量份超過20重量份，則存在因硬化劑分解而產生之氣體導致產生鼓出、龜裂等情況。於硬化劑相對於酚醛清漆型酚系樹脂100重量份未達5重量份，且可溶酚醛型酚系樹脂之調配較少之情形時，有酚醛清漆樹脂之硬化變得不充分之虞。於此情形時，雖亦可增加可溶酚醛型酚系樹脂之量，但相較於此，較佳為於5重量份~20重量份之範圍內增加硬化劑之調配量。若以上述比率添加硬化劑，則後文所述之糊劑(paste)之硬化時間縮短。 When the amount of the curing agent is more than 20 parts by weight based on 100 parts by weight of the novolak-type phenol-based resin, blasting or cracking may occur due to gas generated by decomposition of the curing agent. When the amount of the curing agent is less than 5 parts by weight based on 100 parts by weight of the novolac type phenol resin, and the preparation of the novolac type phenol resin is small, the curing of the novolak resin is insufficient. In this case, although the amount of the novolac type phenol-based resin may be increased, it is preferable to increase the amount of the curing agent in the range of 5 parts by weight to 20 parts by weight. When the hardener is added in the above ratio, the hardening time of the paste described later is shortened.

作為硬化劑，例如可列舉六亞甲基四胺或羥甲基三聚氰胺、羥甲基脲等。其中，六亞甲基四胺因硬化時間較短，故而較佳。 Examples of the curing agent include hexamethylenetetramine, methylol melamine, methylol urea, and the like. Among them, hexamethylenetetramine is preferred because of its short hardening time.

樹脂黏合劑亦可進而含有5重量份~15重量份之苯酚、甲酚、雙酚A等酚化合物。又，亦可含有1重量份以下之甲醛等醛。進而，若為少量，則亦可含有鹼性觸媒或水分。 The resin binder may further contain 5 parts by weight to 15 parts by weight of a phenol compound such as phenol, cresol or bisphenol A. Further, it may contain 1 part by weight or less of an aldehyde such as formaldehyde. Further, if it is a small amount, it may contain a basic catalyst or moisture.

樹脂黏合劑由於相對於酚醛清漆型酚系樹脂100重量份，含有可溶酚醛型酚系樹脂10重量份~30重量份，故而藉由交聯而形成緻密之立體網狀結構。藉此，樹脂黏合劑與研磨粒牢固結合。若可溶酚醛型酚系樹脂相對於酚醛清漆型酚系樹脂100重量份超過30重量份，則糊劑之黏度變得過低，而難以將糊劑塗佈於線上。若可溶酚醛型酚系樹 脂相對於酚醛清漆型酚系樹脂100重量份未達10重量份，則樹脂黏合劑之硬化速度變慢。因此，難以於短時間內使糊劑硬化，樹脂固定線鋸之生產速度變慢。 Since the resin binder contains 10 parts by weight to 30 parts by weight of the novolac type phenol resin with respect to 100 parts by weight of the novolac type phenol resin, a dense three-dimensional network structure is formed by crosslinking. Thereby, the resin binder is firmly bonded to the abrasive grains. When the amount of the novolak-type phenol-based resin exceeds 30 parts by weight based on 100 parts by weight of the novolak-type phenol-based resin, the viscosity of the paste becomes too low, and it is difficult to apply the paste to the wire. Resolute novolac phenolic tree When the amount of the fat is less than 10 parts by weight based on 100 parts by weight of the novolac type phenol resin, the curing rate of the resin binder is slow. Therefore, it is difficult to harden the paste in a short time, and the production speed of the resin-fixed wire saw becomes slow.

若相對於酚醛清漆型酚系樹脂100重量份調配0.1重量份~5重量份之胺系矽烷偶合劑，則樹脂黏合劑與線之接著強度增加。若胺系矽烷偶合劑相對於酚醛清漆型酚系樹脂100重量份未達0.1重量份，則無法期待接著強度增加。若胺系矽烷偶合劑相對於酚醛清漆型酚系樹脂100重量份超過5重量份，則會對酚醛清漆型酚系樹脂之硬化造成不良影響。 When 0.1 part by weight to 5 parts by weight of the amine decane coupling agent is blended with respect to 100 parts by weight of the novolac type phenol resin, the adhesion strength between the resin binder and the wire increases. When the amine-based decane coupling agent is less than 0.1 part by weight based on 100 parts by weight of the novolak-type phenol-based resin, the increase in the subsequent strength cannot be expected. When the amine decane coupling agent exceeds 5 parts by weight based on 100 parts by weight of the novolac type phenol resin, the curing of the novolac type phenol resin is adversely affected.

作為胺系矽烷偶合劑，可列舉：3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基三乙氧基矽烷等。 Examples of the amine decane coupling agent include 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, and N-2-(amino group). Ethyl)-3-aminopropylmethyldimethoxydecane, 3-aminopropyltriethoxydecane, and the like.

樹脂黏合劑含有酚醛清漆型酚系樹脂：100重量份、可溶酚醛型酚系樹脂：10重量份~30重量份、胺系矽烷偶合劑：0.1重量份~5重量份。藉由使用此種樹脂黏合劑，可獲得切斷性能良好且壽命較長之樹脂固定線鋸。 The resin binder contains a novolac type phenol resin: 100 parts by weight, a novolac type phenol resin: 10 parts by weight to 30 parts by weight, and an amine decane coupling agent: 0.1 parts by weight to 5 parts by weight. By using such a resin binder, a resin-fixed wire saw having good cutting performance and a long life can be obtained.

製造本發明之樹脂固定線鋸之製造方法包括以下步驟：(a)準備糊劑(包含樹脂黏合劑、溶劑、研磨粒、填料)之步驟、(b)準備線之步驟、(c)將糊劑塗佈於線之表面之步驟、(d)對所塗佈之糊劑進行紅外線加熱而使之硬化之步驟。 The manufacturing method of the resin-fixed wire saw of the present invention comprises the steps of: (a) preparing a paste (including a resin binder, a solvent, an abrasive grain, a filler), (b) a step of preparing a wire, and (c) a paste. The step of applying the agent to the surface of the wire, and (d) the step of subjecting the applied paste to infrared heating to harden it.

藉由紅外線加熱，樹脂黏合劑之脫水縮合得以迅速進行，從而形成緻密之立體交聯結構。 By infrared heating, the dehydration condensation of the resin binder proceeds rapidly, thereby forming a dense three-dimensional crosslinked structure.

藉由分配法或浮動模法等，將糊劑塗佈於移行之線上。將糊劑之塗佈量設為使研磨粒之集中度達到50~120。所謂研磨粒之集中度，係研磨粒之面積占線表面之投影面積之比率。於本說明書中，於總投影面積中研磨粒所占之投影面積為15%時，將集中度設為100。 例如，於總投影面積中研磨粒所占之投影面積為30%時集中度為200，於總投影面積中研磨粒所占之投影面積為7.5%時集中度為50。 The paste is applied to the migration line by a dispensing method, a floating mold method, or the like. The coating amount of the paste is set such that the concentration of the abrasive grains reaches 50 to 120. The concentration of the abrasive particles is the ratio of the area of the abrasive particles to the projected area of the surface of the wire. In the present specification, when the projected area occupied by the abrasive grains in the total projected area is 15%, the concentration is set to 100. For example, when the projected area occupied by the abrasive grains in the total projected area is 30%, the degree of concentration is 200, and when the projected area occupied by the abrasive grains is 7.5% in the total projected area, the degree of concentration is 50.

糊劑之黏度係於樹脂黏合劑中加入溶劑而使之成為3Pa‧s~6Pa‧s。溶劑之量較佳為相對於樹脂黏合劑100重量份為100重量份~200重量份之範圍。溶劑並無特別限定，若考慮到反應性，則較佳為低沸點之鄰甲酚。 The viscosity of the paste is such that the solvent is added to the resin binder to make it 3 Pa ‧ 6 6 ‧ s. The amount of the solvent is preferably in the range of 100 parts by weight to 200 parts by weight based on 100 parts by weight of the resin binder. The solvent is not particularly limited, and in view of reactivity, o-cresol having a low boiling point is preferred.

研磨粒並無特別限定，可使用金剛石研磨粒、CBN研磨粒、氧化鋁研磨粒、碳化矽研磨粒等。 The abrasive grains are not particularly limited, and diamond abrasive grains, CBN abrasive grains, alumina abrasive grains, cerium carbide abrasive grains, and the like can be used.

金剛石研磨粒由於導熱率較高，故而於紅外線加熱時，研磨粒之影之部分之溫度亦迅速上升。藉此，樹脂黏合劑之硬化得以均勻進行，因此較佳為使用金剛石研磨粒。研磨粒之尺寸可根據目的、或根據線徑而選擇，但為了減小截口損失(切斷裕度)，較佳為數μm~25μm。作為研磨粒，亦較佳為經鎳或鈦等金屬膜被覆之金剛石研磨粒。然而，由於經銅膜被覆之金剛石研磨粒因銅原子而導致矽太陽電池之效率降低，故而欠佳。與電鍍法線鋸相比，使用鎳膜被覆金剛石研磨粒之樹脂固定線鋸所切斷之矽晶圓之翹曲或鋸痕(saw mark)較少。 Since the diamond abrasive grains have a high thermal conductivity, the temperature of the portion of the abrasive grains is also rapidly increased when heated by infrared rays. Thereby, the hardening of the resin binder is performed uniformly, and therefore it is preferred to use diamond abrasive grains. The size of the abrasive grains can be selected according to the purpose or according to the wire diameter, but in order to reduce the kerf loss (cutting margin), it is preferably several μm to 25 μm. As the abrasive grains, diamond abrasive grains coated with a metal film such as nickel or titanium are also preferable. However, since the diamond abrasive grains coated with the copper film are degraded due to copper atoms, the efficiency of the solar cell is lowered. The warpage or saw mark of the tantalum wafer cut by the resin-fixed wire saw coated with the diamond abrasive grains using a nickel film is less than that of the electroplated wire saw.

為了避免因矽屑所致之堵塞，較理想為研磨粒適度分散於線表面。研磨粒較佳為相對於樹脂黏合劑100重量份，調配50重量份~120重量份。 In order to avoid clogging due to swarf, it is preferred that the abrasive particles are moderately dispersed on the surface of the wire. The abrasive grains are preferably blended in an amount of from 50 parts by weight to 120 parts by weight based on 100 parts by weight of the resin binder.

作為線，較佳為鋼線。線徑並無特別限定，較佳為0.05mm ~0.3mm 。作為鋼線，適宜為由高碳鋼或中碳低合金鋼等熱處理彈簧鋼製成之線材，由硬鋼線、鋼琴線或不鏽鋼線、冷軋鋼線或油回火鋼線等加工彈簧鋼製成之線材，低合金鋼、中合金鋼、高合金鋼、麻時效鋼等高韌性、高疲勞強度之鋼線材。 As the wire, a steel wire is preferred. The wire diameter is not particularly limited, and is preferably 0.05 mm. ~0.3mm . As the steel wire, it is suitable for the wire made of heat-treated spring steel such as high carbon steel or medium carbon low alloy steel. It is made of hard steel wire, piano wire or stainless steel wire, cold rolled steel wire or oil tempered steel wire. High-toughness, high fatigue strength steel wire, such as wire rod, low alloy steel, medium alloy steel, high alloy steel, and aging steel.

一面使塗佈有糊劑之線移行一面進行紅外線加熱，而使糊劑硬 化。由於先前之藉由琺瑯烤爐等進行熱風加熱之情形時自糊劑之表面發生熱硬化，故而存在由反應而產生之水被封入糊劑內部而產生氣泡之情況。相對於此，於對糊劑進行紅外線加熱之情形時由於波長1μm左右之近紅外線被水高效吸收，故而於短時間內完成交聯聚合。於對糊劑進行紅外線加熱之情形時由於水於短時間內蒸發，故而糊劑中不易產生氣泡。紅外線較佳為於波長0.7μm~2.5μm之近紅外線之頻帶具有光譜之波峰者。波長約1μm(0.9μm~1.3μm)之近紅外線由於可抑制所產生之水之汽化所隨之產生之氣泡，故而尤佳。 While the line coated with the paste is moved while performing infrared heating, the paste is hard Chemical. In the case where the hot air is heated by a crucible oven or the like in the past, the surface of the paste is thermally hardened, so that water generated by the reaction is sealed inside the paste to generate bubbles. On the other hand, when the paste is subjected to infrared heating, the near-infrared rays having a wavelength of about 1 μm are efficiently absorbed by water, so that crosslinking polymerization is completed in a short time. In the case where the paste is subjected to infrared heating, since water evaporates in a short time, bubbles are less likely to be generated in the paste. The infrared ray preferably has a peak of a spectrum in a frequency band of near-infrared rays having a wavelength of 0.7 μm to 2.5 μm. The near-infrared rays having a wavelength of about 1 μm (0.9 μm to 1.3 μm) are particularly preferable since they suppress bubbles generated by vaporization of the generated water.

藉由紅外線加熱，與熱風加熱相比高速進行硬化反應，可獲得均勻之高次結構。其結果，硬化後之樹脂黏合劑中，藉由利用MALDI-TOF-MS法進行之質量分析，於陽離子中檢測出顯示208(m/z)間隔之片段之波峰。又，藉由示差熱分析(DTA)法，於175℃~182℃檢測出相當於軟化點之明確之波峰。再者，波峰之溫度因示差熱分析時之升溫速度等而稍有不同。示差熱分析中之波峰反映出顯示208(m/z)間隔之片段之波峰以及均勻之高次結構。藉由均勻之高次結構，樹脂黏合劑之硬度增大，而牢固地保持研磨粒。藉此可獲得切斷性能優異之樹脂固定線鋸。 By the infrared heating, the hardening reaction is performed at a higher speed than the hot air heating, and a uniform high-order structure can be obtained. As a result, in the resin binder after hardening, a peak showing a fragment of 208 (m/z) interval was detected in the cation by mass analysis by the MALDI-TOF-MS method. Further, a clear peak corresponding to the softening point was detected at 175 ° C to 182 ° C by differential thermal analysis (DTA). Further, the temperature of the peak is slightly different depending on the temperature increase rate at the time of differential thermal analysis. The peaks in the differential thermal analysis reflect peaks showing a segment of 208 (m/z) spacing and a uniform high order structure. By uniform high-order structure, the hardness of the resin binder is increased, and the abrasive grains are firmly held. Thereby, a resin-fixed wire saw excellent in cutting performance can be obtained.

圖1係對塗佈有糊劑之線進行紅外線加熱之說明圖。圖1之方法中，使用半筒型之凹面鏡2、及配置於凹面鏡2之長度方向上之直線狀之紅外線加熱器4。使塗佈有糊劑之線3沿凹面鏡2之長度方向(紙面之垂直方向)移行。藉由反射面8反射來自紅外線加熱器4之紅外線，使之聚光於約10mm 之聚光部6(加熱區域)。亦可以包圍線3之移行路徑之方式配置複數個凹面鏡2與紅外線加熱器4。 Fig. 1 is an explanatory view showing infrared heating of a line coated with a paste. In the method of Fig. 1, a semi-cylindrical concave mirror 2 and a linear infrared heater 4 disposed in the longitudinal direction of the concave mirror 2 are used. The line 3 coated with the paste is moved in the longitudinal direction of the concave mirror 2 (the vertical direction of the paper surface). The infrared rays from the infrared heater 4 are reflected by the reflecting surface 8 to be condensed at about 10 mm. Condenser 6 (heating zone). A plurality of concave mirrors 2 and infrared heaters 4 may be disposed in such a manner as to surround the migration path of the line 3.

聚光部6之長度取決於紅外線加熱器4或凹面鏡2之尺寸或個數。使塗佈有糊劑之線3移行，而對糊劑進行紅外線加熱。將聚光部6之長度設為例如400mm~1000mm。為了增長聚光部6，亦可於線3之移行 方向(紙面之垂直方向)上串聯配置複數個紅外線加熱器4。 The length of the concentrating portion 6 depends on the size or the number of the infrared heater 4 or the concave mirror 2. The line 3 coated with the paste is moved, and the paste is heated by infrared rays. The length of the condensing unit 6 is set to, for example, 400 mm to 1000 mm. In order to grow the concentrating part 6, it is also possible to move on line 3. A plurality of infrared heaters 4 are arranged in series in the direction (the vertical direction of the paper surface).

作為紅外線加熱器4，較佳為於近紅外線區域具有波峰之紅外線燈。作為紅外線燈，例如可使用短弧氙燈(short-arc xenon lamp)、或於石英玻璃管中封入鎢絲而成之燈。 As the infrared heater 4, an infrared lamp having a crest in the near-infrared region is preferable. As the infrared lamp, for example, a short-arc xenon lamp or a lamp in which a tungsten wire is sealed in a quartz glass tube can be used.

測定於聚光部6內移行之線3之溫度較為困難。因此，著眼於因加熱導致線3之斷裂強度降低之情況，而設為可確保加熱前之斷裂強度之95%的加熱溫度。利用1mm徑之細速(Sheath type)型熱電偶實驗性地測定聚光部6之溫度，結果為500℃~800℃。使用圖1之紅外線加熱裝置，使線以1,000mm/sec~2,000mm/sec之速度移行，可不使樹脂黏合劑發泡而將其硬化。 It is difficult to measure the temperature of the line 3 which is moved in the concentrating portion 6. Therefore, attention is paid to the case where the breaking strength of the wire 3 is lowered by heating, and it is set as the heating temperature which can ensure 95% of the breaking strength before heating. The temperature of the concentrating portion 6 was experimentally measured by a Sheath type thermocouple having a diameter of 1 mm, and as a result, it was 500 ° C to 800 ° C. The infrared heating device of Fig. 1 is used to move the wire at a speed of 1,000 mm/sec to 2,000 mm/sec, and the resin adhesive can be hardened without foaming.

作為紅外線加熱方法，亦可為照射紅外線雷射之方法。 As the infrared heating method, a method of irradiating an infrared laser may be employed.

於糊劑中調配包含無機粒子之填料(filler)。填料抑制樹脂黏合劑之熱膨脹、熱收縮，減少切斷過程中之研磨粒之脫落。填料較佳為相對於樹脂黏合劑100重量份，調配20重量份~100重量份，進而較佳為調配30重量份~60重量份。作為填料，宜係大小為2μm~3μm左右之金剛石微粒，但亦可使用其他無機材料(例如碳化矽微粒)。 A filler containing inorganic particles is formulated in the paste. The filler inhibits thermal expansion and heat shrinkage of the resin binder, and reduces the shedding of the abrasive grains during the cutting process. The filler is preferably formulated in an amount of 20 parts by weight to 100 parts by weight based on 100 parts by weight of the resin binder, and more preferably 30 parts by weight to 60 parts by weight. As the filler, diamond particles having a size of about 2 μm to 3 μm are preferable, but other inorganic materials (for example, niobium carbide particles) may be used.

若對實施紅外線加熱之樹脂固定線鋸進行再加熱，則性能穩定。藉由再加熱，可去除於紅外線加熱時線及糊劑所產生之熱應變。幾乎不存在因再加熱而導致樹脂固定線鋸之斷裂應力、或樹脂黏合劑之分子結構發生變化之情況。 If the resin-fixed wire saw that performs infrared heating is reheated, the performance is stable. By reheating, the thermal strain generated by the wire and the paste during infrared heating can be removed. There is almost no change in the fracture stress of the resin-fixed wire saw due to reheating or the molecular structure of the resin binder.

再加熱較佳為於溫度100℃~200℃下進行1小時~5小時。雖然再加熱之時間較長，但由於一次可對較多之捲繞有樹脂固定線鋸之線軸進行再加熱，故而不存在因再加熱而導致樹脂固定線鋸之生產性大幅降低之情況。藉由將紅外線加熱與再加熱加以組合，可獲得樹脂固定線鋸之較高之生產性。 The reheating is preferably carried out at a temperature of from 100 ° C to 200 ° C for from 1 hour to 5 hours. Although the reheating time is long, since the bobbin wound with a large number of resin-fixed wire saws can be reheated at a time, there is no possibility that the productivity of the resin-fixed wire saw is greatly lowered by reheating. By combining infrared heating and reheating, a higher productivity of the resin-fixed wire saw can be obtained.

與先前之樹脂固定線鋸相比，本發明之樹脂固定線鋸之切口深 度較大。所謂「切口深度」，係指對試樣進行切割、線鋸斷線時之切口深度。線鋸之斷線主要係因研磨粒之脫落而引起。本發明之樹脂固定線鋸與先前之樹脂固定線鋸相比，研磨粒之固定強度較大，故而切口深度較大。 The depth of the slit of the resin-fixed wire saw of the present invention is deeper than that of the prior resin-fixed wire saw Larger. The term "notch depth" refers to the depth of the cut when the sample is cut and the wire saw is broken. The wire break of the wire saw is mainly caused by the falling off of the abrasive grains. The resin-fixed wire saw of the present invention has a larger fixing strength of the abrasive grains than the prior resin-fixed wire saw, and thus the depth of the slit is large.

關於本發明之樹脂固定線鋸，其晶圓之翹曲、起伏、厚度變動值(TTV，total thickness variation)中之任一者與先前之樹脂固定線鋸相比均優異25%以上。藉由本發明之樹脂固定線鋸，可獲得面粗度(Ra、Ry)之值較先前之樹脂固定線鋸小20%左右之晶圓。藉由本發明之樹脂固定線鋸，可獲得表面之加工變質層較少之晶圓。藉由本發明之樹脂固定線鋸，可獲得彎曲強度較高之晶圓。 Regarding the resin-fixed wire saw of the present invention, any of the warpage, undulation, and thickness variation (TTV) of the wafer is superior to that of the conventional resin-fixed wire saw by 25% or more. By the resin-fixed wire saw of the present invention, it is possible to obtain a wafer having a surface roughness (Ra, Ry) which is about 20% smaller than that of the prior art resin-fixed wire saw. By the resin-fixed wire saw of the present invention, it is possible to obtain a wafer having a small number of processed metamorphic layers on the surface. With the resin-fixed wire saw of the present invention, a wafer having a high bending strength can be obtained.

[實施例] [Examples]

本發明之樹脂固定線鋸之切斷性能係藉由以下之實驗而得以確認。 The cutting performance of the resin-fixed wire saw of the present invention was confirmed by the following experiment.

使用下述調配成分之樹脂黏合劑，調整如下調配成分之糊劑，並藉由如下生產線製造樹脂固定線鋸。 The paste of the following formulation was adjusted using the resin binder of the following formulation, and the resin-fixed wire saw was manufactured by the following production line.

[實施例1] [Example 1] (1)樹脂黏合劑之調配成分 (1) Formulation of resin binder

(2)糊劑之調配成分 (2) Formulation of paste

(3)樹脂固定線鋸之生產線 (3) Resin fixed wire saw production line

(a)生產線之概要 (a) Summary of the production line

線捲出機→塗佈裝置→加熱裝置→捲取機→再加熱爐 Wire winding machine→Coating device→Heating device→Winding machine→Reheating furnace

(b)線捲出機：將捲繞於線軸上之線捲出之裝置。 (b) Wire take-up machine: A device that winds a wire wound on a bobbin.

(c)塗佈裝置：利用水刀狀之模具於線表面均勻地塗佈糊劑之裝置。 (c) Coating device: A device in which a paste is uniformly applied to a surface of a wire by a water knife-shaped mold.

(d)加熱裝置：對塗佈有糊劑之線進行加熱之裝置。 (d) Heating means: means for heating the line coated with the paste.

串聯3個ULVAC理工股份有限公司製造之紅外線高溫聚光爐(infrared gold image furnace)：型號RHL-E410-N(加熱長度265mm，最大輸出4kw)而使用。圖2表示燈之能量分光分佈。 Infrared gold image furnace manufactured by three ULVAC Technology Co., Ltd. series: model RHL-E410-N (heating length 265mm, maximum output 4kw) is used. Figure 2 shows the energy splitting distribution of the lamp.

(e)捲取機：將樹脂固定線鋸捲取至線軸上之裝置。 (e) Coiler: A device that winds a resin-fixed wire saw onto a bobbin.

(f)再加熱爐：對利用捲取機捲取至線軸上之樹脂固定線鋸進行加熱之對流式加熱爐。 (f) Reheating furnace: a convection heating furnace that heats a resin-fixed wire saw wound on a bobbin by a coiler.

(4)材料及製造條件 (4) Materials and manufacturing conditions

(a)線：鋼琴線(線徑：120μm，斷裂強度：約42N)。 (a) Line: Piano line (wire diameter: 120 μm, breaking strength: about 42 N).

(b)線之移行速度：1200mm/sec。 (b) Line travel speed: 1200 mm/sec.

(c)糊劑之塗佈量：0.01g/m。 (c) Coating amount of paste: 0.01 g/m.

(d)紅外線高溫聚光爐之溫度：720℃~750℃(熱電偶測定)。 (d) Temperature of infrared high-temperature concentrating furnace: 720 ° C ~ 750 ° C (thermocouple measurement).

(不使樹脂固定線鋸之斷裂強度未達40N之溫度) (Do not make the resin fixed wire saw fracture strength less than 40N)

(e)再加熱爐中之溫度與時間：180℃、2小時。 (e) Temperature and time in the reheating furnace: 180 ° C, 2 hours.

[實施例2] [Embodiment 2] (1)樹脂黏合劑之調配成分 (1) Formulation of resin binder

(2)糊劑之調配成分 (2) Formulation of paste

除上述以外，以與實施例1相同之方式製造樹脂固定線鋸。 A resin-fixed wire saw was produced in the same manner as in Example 1 except the above.

[比較例] [Comparative example]

作為樹脂黏合劑，使用市售之酚醛清漆型酚系樹脂(SUMITOMO BAKELITE公司製造)，作為加熱裝置，使用豎型琺瑯烤爐。豎型琺瑯烤爐係藉由循環於爐芯管內之加熱空氣而對線進行加熱。發熱體為鎳鉻合金線。於豎型琺瑯烤爐中，進行爐溫300℃、加熱時間20分鐘之加熱。除此以外，以與實施例1相同之方式獲得樹脂固定線鋸。 As a resin binder, a commercially available novolac type phenol resin (manufactured by SUMITOMO BAKELITE Co., Ltd.) was used, and a vertical oven was used as a heating device. Vertical ovens heat the wire by circulating heated air within the furnace tube. The heating element is a nickel-chromium alloy wire. In a vertical oven, heating was carried out at a furnace temperature of 300 ° C and a heating time of 20 minutes. Except for this, a resin-fixed wire saw was obtained in the same manner as in Example 1.

將實施例1、2之樹脂固定線鋸之切口深度與比較例之樹脂固定線鋸之切口深度進行比較。 The depth of the slit of the resin-fixed wire saw of Examples 1 and 2 was compared with the depth of the slit of the resin-fixed wire saw of the comparative example.

(1)切口深度試驗方法 (1) Incision depth test method

將1cm×1cm×2mm之多晶矽片設置於水平拉伸之樹脂固定線鋸之上方，使多晶矽片下降移動，測定切口深度。矽片之下降速度： 0.9mm/min。 A polycrystalline ruthenium sheet of 1 cm × 1 cm × 2 mm was placed over the horizontally stretched resin-fixed wire saw, and the polycrystalline enamel sheet was moved downward to measure the depth of the slit. The falling speed of the film: 0.9mm/min.

(2)切割條件 (2) Cutting conditions

樹脂黏合劑線運動：振幅80mm、速度400mm/min之往復運動。 Resin adhesive line movement: reciprocating motion with an amplitude of 80 mm and a speed of 400 mm/min.

(3)切割時間：直至斷線。 (3) Cutting time: until the line is broken.

表1表示切口深度試驗之結果。表2表示試驗後之線之研磨粒殘存率。 Table 1 shows the results of the incision depth test. Table 2 shows the residual ratio of the abrasive grains of the wire after the test.

如表1所示，實施例1、2之樹脂固定線鋸之切口深度為比較例之樹脂固定線鋸之切口深度的約1.7倍。如表2所示，實施例1之樹脂固定線鋸之研磨粒殘存率為比較例之樹脂固定線鋸之研磨粒殘存率的約1.8倍。 As shown in Table 1, the depth of the slit of the resin-fixed wire saw of Examples 1 and 2 was about 1.7 times the depth of the slit of the resin-fixed wire saw of the comparative example. As shown in Table 2, the residual ratio of the abrasive grains of the resin-fixed wire saw of Example 1 was about 1.8 times that of the resin-fixed wire saw of the comparative example.

為了研究該差之原因，對經硬化之樹脂黏合劑之硬度進行研究。 In order to investigate the cause of the difference, the hardness of the cured resin binder was investigated.

實例1：對實施例1所使用之樹脂黏合劑進行加熱硬化。加熱條件：以15℃/小時自室溫升溫至180℃，並於180℃下保持2小時。 Example 1: The resin binder used in Example 1 was heat-hardened. Heating conditions: The temperature was raised from room temperature to 180 ° C at 15 ° C / hour, and maintained at 180 ° C for 2 hours.

實例2：於與實例1相同之加熱條件下對比較例所使用之酚醛清漆型酚系樹脂進行加熱硬化。 Example 2: The novolac type phenol-based resin used in the comparative example was heat-hardened under the same heating conditions as in Example 1.

使用明石製作所製造之硬度計(ATK-F3000；使用1/4吋鋼球、荷重100kgf)，對所獲得之硬化物之硬度的洛氏硬度(Rockwell hardness)進行測定。將結果示於表3中。 A Rockwell hardness of the hardness of the obtained cured product was measured using a hardness meter (ATK-F3000; using a 1/4 inch steel ball and a load of 100 kgf) manufactured by Akashi Seisakusho Co., Ltd. The results are shown in Table 3.

由表3可知，與比較例之樹脂黏合劑相比，實施例1之樹脂黏合劑之硬度較高。其係本發明之樹脂固定線鋸之切口深度較深之原因之一。 As is clear from Table 3, the hardness of the resin binder of Example 1 was higher than that of the resin binder of the comparative example. It is one of the reasons why the depth of the slit of the resin-fixed wire saw of the present invention is deep.

[分析] [analysis]

對實施例1之樹脂黏合劑及比較例之樹脂黏合劑之網狀分子結構與物性進行研究。 The network structure and physical properties of the resin binder of Example 1 and the resin binder of Comparative Example were investigated.

藉由MALDI-TOF-MS法進行質量分析。(MALDI：基質輔助雷射脫附游離法，TOF-MS：飛行時間型質譜法)。 Mass analysis was performed by the MALDI-TOF-MS method. (MALDI: matrix-assisted laser desorption free method, TOF-MS: time-of-flight mass spectrometry).

‧使用設備：島津製作所製造之AXIMA-CFR+(SHIMADZU)。 ‧ Equipment used: AXIMA-CFR + (SHIMADZU) manufactured by Shimadzu Corporation.

‧分析模式：線性模式(陽離子、陰離子檢測)。 ‧ Analysis mode: linear mode (cation, anion detection).

‧真空度：10-5Pa以下。 ‧ Vacuum degree: 10 -5 Pa or less.

‧基質：2,5-二羥基苯甲酸。 ‧ Matrix: 2,5-dihydroxybenzoic acid.

‧雷射波長：337nm(氮氣雷射)。 ‧Laser wavelength: 337 nm (nitrogen laser).

圖3~圖6表示利用MALDI-TOF-MS法進行之質量分析之測定圖表。圖3係比較例之樹脂黏合劑之陽離子檢測圖表。圖4係實施例1之樹脂黏合劑之陽離子檢測圖表。圖5係比較例之樹脂黏合劑之陰離子檢測圖表。圖6係實施例1之樹脂黏合劑之陰離子檢測圖表。 3 to 6 show measurement charts of mass analysis by the MALDI-TOF-MS method. Fig. 3 is a chart showing the cation detection of the resin binder of the comparative example. Fig. 4 is a chart showing the cation detection of the resin binder of Example 1. Fig. 5 is an anion detection chart of a resin binder of a comparative example. Fig. 6 is an anion detecting chart of the resin binder of Example 1.

圖4(實施例1)中可見顯示208(m/z)間隔之片段之波峰(箭頭)。推測208(m/z)間隔之片段係下述結構式(結構單元；C14H12O2：分子量212)中，因於含有芳香環之4個部位交聯裂解(片段)而產生者。 A peak (arrow) showing a segment of the 208 (m/z) interval can be seen in Fig. 4 (Example 1). It is presumed that the fragment of the 208 (m/z) interval is produced by cross-linking cleavage (fragment) of four sites containing an aromatic ring in the following structural formula (structural unit; C 14 H 12 O 2 : molecular weight 212).

[化1] [Chemical 1]

其揭示出於實施例1之樹脂黏合劑中，下述結構作為重複片段而有序排列為網狀高分子結構。 It is revealed that in the resin binder of Example 1, the following structures are arranged as a repeating segment and are arranged in a network structure.

圖3、圖5、圖6中未檢測出顯示固定間隔之片段之波峰(箭頭)。因此，認為比較例之樹脂黏合劑中不存在化學式1所表示之結構。 In Fig. 3, Fig. 5, and Fig. 6, the peaks (arrows) showing the segments of the fixed interval are not detected. Therefore, it is considered that the structure represented by Chemical Formula 1 does not exist in the resin binder of the comparative example.

根據與圖3~圖6相關之上述結果，認為顯示208(m/z)間隔之片段之分子結構係因對樹脂黏合劑進行紅外線加熱而產生者。 Based on the above results relating to FIGS. 3 to 6, it is considered that the molecular structure of the segment at intervals of 208 (m/z) is generated by infrared heating of the resin binder.

圖7表示實施例1之樹脂黏合劑及比較例之樹脂黏合劑之示差熱分析圖表。 Fig. 7 is a graph showing the differential thermal analysis of the resin binder of Example 1 and the resin binder of Comparative Example.

‧使用裝置：TG8120(Rigaku)。 ‧Use device: TG8120 (Rigaku).

‧升溫速度：10℃/min(分鐘)。 ‧ Heating rate: 10 ° C / min (minutes).

‧環境：氮氣氣流。 ‧Environment: Nitrogen gas flow.

‧標準物質：氧化鋁(Al2O3)。 ‧Standard material: alumina (Al 2 O 3 ).

‧試樣重量：約10mg。 ‧ Sample weight: about 10 mg.

於圖7所示之實施例1之樹脂黏合劑的圖表中，於175℃~182℃可見明確之軟化點之波峰。相對於此，比較例之樹脂黏合劑只不過於190℃附近可見不明確之軟化點之波峰。比較例之樹脂黏合劑由於高 次結構不均，故而認為不會發生伴隨結構變化之轉移，而無法觀察到明確之軟化點之波峰。實施例1之樹脂黏合劑由於具有由208(m/z)間隔之片段所形成之高次結構，故而認為硬度較高。認為比較例之樹脂黏合劑之硬度較低之原因係由高次結構不均所致。 In the graph of the resin binder of Example 1 shown in Fig. 7, a clear peak of the softening point was observed at 175 ° C to 182 ° C. On the other hand, the resin binder of the comparative example showed only a peak of an unclear softening point near 190 °C. The resin adhesive of the comparative example is high The secondary structure is uneven, so it is considered that there is no transfer accompanying the structural change, and a clear peak of the softening point cannot be observed. The resin binder of Example 1 has a high hardness because it has a high-order structure formed of a segment having a spacing of 208 (m/z). The reason why the hardness of the resin binder of the comparative example is low is considered to be caused by high-order structural unevenness.

[產業上之可利用性] [Industrial availability]

若使用本發明之樹脂固定線鋸，則可自矽晶錠高效地切割出高品質之晶圓。 When the resin-fixed wire saw of the present invention is used, high-quality wafers can be efficiently cut from the ingot.

Claims (2)

一種樹脂固定線鋸，其係藉由以酚系樹脂為主成分之樹脂黏合劑而將研磨粒固定於線之表面者，且上述樹脂黏合劑於利用MALDI-TOF-MS法進行之質量分析中，陽離子中顯示出表示208(m/z)間隔之片段之複數個波峰，於利用TG-DTA法進行之示差熱分析中，於175℃~182℃顯示出相當於軟化點之波峰。 A resin-fixed wire saw which fixes abrasive grains to a surface of a wire by a resin binder containing a phenol resin as a main component, and the above-mentioned resin binder is subjected to mass analysis by MALDI-TOF-MS method In the cation, a plurality of peaks indicating a fragment at intervals of 208 (m/z) were shown, and in the differential thermal analysis by the TG-DTA method, a peak corresponding to the softening point was exhibited at 175 ° C to 182 ° C. 如請求項1之樹脂固定線鋸，其中上述樹脂黏合劑含有酚醛清漆型酚系樹脂100重量份、可溶酚醛型酚系樹脂10重量份~30重量份、及胺系矽烷偶合劑0.1重量份~5重量份。 The resin-fixed wire saw according to claim 1, wherein the resin binder contains 100 parts by weight of a novolac type phenol-based resin, 10 parts by weight to 30 parts by weight of a novolac type phenol-based resin, and 0.1 part by weight of an amine-based decane coupling agent. ~5 parts by weight.
TW102146989A 2013-01-10 2013-12-18 Resin fixed wire saws TWI519366B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2013002792A JP5792208B2 (en) 2013-01-10 2013-01-10 Resin bond wire saw

Publications (2)

Publication Number Publication Date
TW201433391A TW201433391A (en) 2014-09-01
TWI519366B true TWI519366B (en) 2016-02-01

Family

ID=51166811

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102146989A TWI519366B (en) 2013-01-10 2013-12-18 Resin fixed wire saws

Country Status (7)

Country Link
JP (1) JP5792208B2 (en)
KR (1) KR101594747B1 (en)
CN (1) CN104918752B (en)
MY (1) MY168372A (en)
SG (1) SG11201504210SA (en)
TW (1) TWI519366B (en)
WO (1) WO2014109149A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201708638PA (en) * 2015-04-20 2017-11-29 Tkx Corp Method for producing fine silicon powder, and method for producing fine silicon nitride powder
WO2016186075A1 (en) * 2015-05-21 2016-11-24 三井化学東セロ株式会社 Method for manufacturing gas-barrier layered product
WO2017203801A1 (en) * 2016-05-24 2017-11-30 株式会社Tkx Device for manufacturing coated wire

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR940001070B1 (en) * 1990-12-29 1994-02-12 고려화학 주식회사 Preparation of epoxy resin compositions for encapsulating semiconductor
JP3734854B2 (en) 1995-07-18 2006-01-11 古河電気工業株式会社 Hot air circulation type individual multiple enamel wire baking furnace and method for producing enamel wire using the same
KR100306358B1 (en) * 1997-02-14 2001-11-30 추후보충 File Saws and Manufacturing Methods
JP2000263452A (en) 1999-03-12 2000-09-26 Osaka Diamond Ind Co Ltd Super-abrasive grain wire saw
JP2000271872A (en) 1999-03-23 2000-10-03 Osaka Diamond Ind Co Ltd Super abrasive grain resin bond wire saw
JP2001259993A (en) * 2000-03-10 2001-09-25 Noritake Diamond Ind Co Ltd Resin bond wire saw
JP2008006584A (en) * 2000-05-15 2008-01-17 Allied Material Corp Cutting method using super-abrasive grain wire saw
JP2003334763A (en) 2002-05-16 2003-11-25 Read Co Ltd Fixed abrasive grain wire saw
US7435276B2 (en) * 2003-05-09 2008-10-14 Diamond Innovations, Inc. Abrasive particles having coatings with tortuous surface topography
JP2006123024A (en) 2004-10-26 2006-05-18 Nakamura Choko:Kk Fixed abrasive grain type wire saw and its manufacturing method
JP4703448B2 (en) * 2006-03-22 2011-06-15 株式会社ノリタケスーパーアブレーシブ Resin bond wire saw
JP2008103690A (en) 2007-08-24 2008-05-01 Mitsubishi Electric Corp Slurry used for cutting silicon ingot
CN101712135B (en) * 2008-09-30 2014-07-02 日本则武超精密磨料磨具有限公司 Resin bonder wire saw
CN101445587B (en) * 2008-12-26 2011-11-16 南京师范大学 Resin binding agent for a diamond wire saw and preparation method thereof
JP5443825B2 (en) 2009-05-15 2014-03-19 古河電気工業株式会社 Enamel wire printing equipment
CN102513609B (en) * 2011-12-28 2013-09-25 山东大学 Resin bond consolidation abrasive wire saw production system

Also Published As

Publication number Publication date
TW201433391A (en) 2014-09-01
CN104918752A (en) 2015-09-16
CN104918752B (en) 2016-04-20
WO2014109149A1 (en) 2014-07-17
KR20150102946A (en) 2015-09-09
JP5792208B2 (en) 2015-10-07
KR101594747B1 (en) 2016-02-16
MY168372A (en) 2018-10-31
SG11201504210SA (en) 2015-07-30
JP2014133288A (en) 2014-07-24

Similar Documents

Publication Publication Date Title
TWI519366B (en) Resin fixed wire saws
US9597734B2 (en) Electrostatic chuck and showerhead with enhanced thermal properties and methods of making thereof
CN112218824A (en) Graphene-based heat removal device and method for manufacturing same
JP5116855B2 (en) Wafer heating device, electrostatic chuck
TW201036762A (en) Superabrasive tool having surface modified superabrasive particles and associated methods
CN1977378A (en) Aluminum-silicon carbide composite
TWI527666B (en) A method for manufacturing an adhesive composition for a resin bonded wire saw, and a method for manufacturing a resin bonded wire saw
CN105171943B (en) A kind of pbo fiber resin diamond wire and preparation method thereof
JP2004009239A (en) Saw wire manufacturing method
JP5899443B2 (en) Thermosetting adhesive for fixing silicon ingot, silicon ingot fixing method using the same, and silicon wafer manufacturing method
JP2010131997A (en) Thermosetting material, and method and device for forming set or unset thermosetting material
TW201705556A (en) Heat dissipating substrate, device, and manufacturing method of heat dissipating substrate
JP2020012194A (en) Metal-silicon carbide composite and production method of the same
WO2022030390A1 (en) Method for producing multilayer body, multilayer body and method for producing semiconductor package
CN111500250A (en) Preparation method of heat-resistant adhesive
JP2020015879A (en) Peelable scale attachment prevention material, inorganic member having peelable scale attachment prevention layer, and scale attachment prevention method
JP2023127000A (en) Production method of multilayer body, multilayer body, and production method of semiconductor package
JP5542738B2 (en) Wire tool manufacturing method
CN108115854B (en) Resin diamond wire and preparation method thereof
JPWO2017209242A1 (en) Resin bond wire saw and its manufacturing method
WO2020202970A1 (en) Bonded body and method for manufacturing same
TWI582370B (en) Method for Making High Thermal Conductivity Elements
SU1161307A1 (en) Method of manufacturing multiblade disc tool
JP2013223902A (en) Cutting blade and its manufacturing method
JPS61163915A (en) Production of solid resol phenolic resin

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees