TW202012105A - Polishing pad and method for producing the same capable of shortening time required for run-in and reducing defects at the initial stage of polishing - Google Patents
Polishing pad and method for producing the same capable of shortening time required for run-in and reducing defects at the initial stage of polishing Download PDFInfo
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Description
本發明是有關於一種研磨墊。詳細而言，本發明是有關於一種可用於光學材料、半導體晶圓、半導體器件、硬碟用基板等的研磨，特別是可較佳地用於對在半導體晶圓之上形成有氧化物層、金屬層等的器件進行研磨的研磨墊。The invention relates to a polishing pad. In detail, the present invention relates to polishing for optical materials, semiconductor wafers, semiconductor devices, substrates for hard disks, etc., and is particularly suitable for forming oxide layers on semiconductor wafers. , Metal layer and other devices to polish the polishing pad.
隨著積體度的增大，半導體器件正在微細化或多層化。因此，用於半導體器件的玻璃基板等的研磨除了要求生產性以外，亦要求研磨傷的削除（瑕疵（defect）、刮痕（scratch）的抑制）等。As the degree of integration increases, semiconductor devices are being miniaturized or multi-layered. Therefore, in addition to productivity, polishing of glass substrates and the like used for semiconductor devices also requires removal of polishing scratches (defects and suppression of scratches).
作為滿足此種要求的研磨方法，一般在各種研磨方法中採用游離磨粒方式的研磨。游離磨粒方式是一面向研磨墊與被研磨物之間供給包含磨粒的漿料（研磨液）一面對被研磨物的加工面進行研磨加工的方法。As a polishing method that satisfies such requirements, in general, free abrasive grain polishing is used in various polishing methods. The free abrasive method is a method of supplying a slurry (abrasive liquid) containing abrasive particles between the polishing pad and the object to be polished while facing the processing surface of the object to be polished.
在游離磨粒方式的研磨中，在將研磨墊安裝於研磨裝置後，進行實際的研磨之前，一般藉由使用了金剛石磨粒盤等的打磨（dress）處理使研磨墊的表面（研磨面）粗糙化而進行銳化處理。藉由進行打磨處理，可進行實現研磨墊的研磨性能的提高的所謂磨合（break in）（啟用）。為了提高半導體晶圓的生產性，期望縮短所述磨合所需要的時間。In free abrasive grain polishing, after the polishing pad is attached to the polishing device and before actual polishing, the surface (grinding surface) of the polishing pad is generally treated by dressing using a diamond abrasive disc or the like Roughen and sharpen. By performing the grinding process, a so-called break in (enablement) that improves the polishing performance of the polishing pad can be performed. In order to improve the productivity of semiconductor wafers, it is desirable to shorten the time required for the break-in.
在專利文獻1中揭示了一種藉由將研磨墊表面的平均表面粗糙度（Ra）設為1 μm以上且5 μm以下，而可縮短磨合所需要的時間的研磨墊。
[現有技術文獻]
[專利文獻]
[專利文獻1]國際公開第2008/029725號公報[Patent Document 1] International Publication No. 2008/029725
[發明所欲解決之課題] 然而，已知：若只簡單地調整平均表面粗糙度（Ra），則即便可縮短磨合所需要的時間，亦存在其後的研磨初期的瑕疵大，不能呈現所期望的研磨性能的情況。[Problems to be solved by the invention] However, it is known that if the average surface roughness (Ra) is simply adjusted, even if the time required for running-in can be shortened, there may be a large defect in the subsequent initial polishing period, and the desired polishing performance may not be exhibited.
因此，本發明以提供一種縮短磨合所需要的時間並且減少研磨初期的瑕疵的研磨墊為目的。Therefore, the present invention aims to provide a polishing pad that shortens the time required for running-in and reduces defects at the initial stage of polishing.
[解決課題之手段] 本發明者們進行了積極研究，結果發現，藉由實現算術平均高度（Sa）及研磨層表面的峰頂點的主曲率的平均即峰頂點的算術平均曲率（Spc）為規定的範圍內的研磨墊，可縮短磨合時間且可減少瑕疵，從而達成了本發明。即，本發明包括以下內容。 [1] 一種研磨墊，具有研磨被研磨物的研磨層，所述研磨墊的特徵在於，相對於研磨層的研磨面的平均面，表示各點的高度之差的絕對值的平均的算術平均高度（Sa）為3～10（μm），所述研磨面的峰頂點的主曲率的平均即峰頂點的算術平均曲率（Spc）為200～600（1/mm）。 [2] 如[1]所述的研磨墊，其中表示所述研磨面的每單位面積的峰頂點的數量的峰頂點密度（Spd）為2000～6000（1/mm2 ）。 [3] 一種研磨墊的製造方法，其為製造如[1]或[2]所述的研磨墊的方法，包括在紙圓周速度與平台速度之比（紙圓周速度/平台速度）為50～750的條件下實施拋光（buff）處理的步驟。[Means for Solving the Problems] The inventors conducted active research and found that the arithmetic mean curvature (Spc) of the peak apex, which is the average of the arithmetic mean height (Sa) and the main curvature of the peak apex on the surface of the polishing layer, is The polishing pad within the prescribed range can shorten the running-in time and can reduce defects, thereby achieving the present invention. That is, the present invention includes the following. [1] A polishing pad having a polishing layer for polishing an object to be polished, wherein the polishing pad is characterized by an arithmetic average representing an average of absolute values of differences in heights of respective points with respect to an average surface of a polishing surface of the polishing layer The height (Sa) is 3 to 10 (μm), and the average of the main curvatures of the peak apex of the polished surface, that is, the arithmetic mean curvature (Spc) of the peak apex, is 200 to 600 (1/mm). [2] The polishing pad according to [1], wherein the peak apex density (Spd) indicating the number of peak apexes per unit area of the polishing surface is 2000 to 6000 (1/mm 2 ). [3] A method for manufacturing a polishing pad, which is a method for manufacturing a polishing pad as described in [1] or [2], which includes a ratio of paper peripheral speed to platform speed (paper peripheral speed/platform speed) of 50 to Under the conditions of 750, buffing is performed.
[發明的效果] 本發明的研磨墊可縮短磨合時間且可減少研磨初期的瑕疵。[Effect of invention] The polishing pad of the present invention can shorten the running-in time and can reduce defects in the initial stage of polishing.
以下，針對用於實施發明的形態進行說明，但本發明並不僅僅限定於用於實施發明的形態。Hereinafter, the embodiment for carrying out the invention will be described, but the present invention is not limited to the embodiment for carrying out the invention.
在本說明書中，Ra表示在對象表面的平均線的方向上僅提取基準長度l，相對於此提取部分的平均線，各點的高度之差的絕對值的平均，並由日本工業標準（Japanese Industrial Standard，JIS）B 671-1/ISO 13565-1（線粗糙度測定）進行規定。In this specification, Ra means that only the reference length l is extracted in the direction of the average line on the surface of the object, and the average value of the difference in height of each point is averaged with respect to the average line of the extracted part, and is determined by the Japanese Industrial Standard (Japanese Industrial Standard, JIS) B 671-1/ISO 13565-1 (Measurement of Line Roughness) is specified.
在本說明書中，Sa表示相對於表面的基準面，提取基準面積A，各點的高度之差的絕對值的平均。在本說明書中，Sa的單位為（μm）。In this specification, Sa represents the average of the absolute values of the differences in the heights of the points from which the reference area A is extracted with respect to the reference plane of the surface. In this specification, the unit of Sa is (μm).
在本說明書中，Spc表示表面的峰頂點的主曲率的平均。即，研磨層表面的峰頂點的主曲率的平均即峰頂點的算術平均曲率。另外，Spc的值小的情況下表示與其他物體接觸的點帶弧度，Spc的值大的情況下表示與其他物體接觸的點尖起。在本說明書中，Spc的單位為（1/mm）。In this specification, Spc represents the average of the main curvatures of the peak apex of the surface. That is, the average of the main curvatures of the peak apexes on the surface of the polishing layer is the arithmetic average curvature of the peak apex. In addition, when the value of Spc is small, the point of contact with other objects is curved, and when the value of Spc is large, the point of contact with other objects is pointed. In this manual, the unit of Spc is (1/mm).
在本說明書中，Spd表示每單位面積的峰頂點的數量。若此值大，則表示與其他物體的接觸點多。在本說明書中，單位為（1/mm2 ）。In this specification, Spd represents the number of peak apexes per unit area. If this value is large, it means that there are many points of contact with other objects. In this manual, the unit is (1/mm 2 ).
另外，Sa、Spc、Spd均由國際標准化組織（International Organization for Standardization，ISO）25178（三維表面性狀（表面粗糙度））進行規定。In addition, Sa, Spc, and Spd are all specified by the International Organization for Standardization (ISO) 25178 (three-dimensional surface properties (surface roughness)).
＜＜研磨墊＞＞ 針對本發明的研磨墊進行說明。 通常，製造後初次進行研磨的研磨墊在不對研磨面進行表面處理的情況下即便用於研磨，研磨率亦不充分，而難言可恰當地進行研磨。因此，研磨的初期階段反覆進行打磨處理與預備研磨，成為充分的研磨率之後，進行實際的製品的研磨。 但是，在本發明的研磨墊中，即便是完全不進行打磨處理或是比通常的打磨處理時間短的打磨處理，亦能夠以充分的研磨率來進行研磨。＜＜Grinding Pad＞＞ The polishing pad of the present invention will be described. In general, a polishing pad that is polished for the first time after manufacturing is used for polishing without surface treatment of the polishing surface, the polishing rate is insufficient, and it is difficult to say that polishing can be performed properly. Therefore, at the initial stage of polishing, the polishing process and the preliminary polishing are repeatedly performed to achieve a sufficient polishing rate, and then the actual product is polished. However, in the polishing pad of the present invention, even if the polishing treatment is not performed at all or the polishing treatment time is shorter than the usual polishing treatment time, the polishing can be performed at a sufficient polishing rate.
使用圖1～圖3對本發明的研磨墊的結構進行說明。如圖1所示，研磨墊1包含與被研磨物抵接，進行研磨的層即研磨層2。研磨層2具有與被研磨物抵接的研磨面2a。本發明的研磨墊1的研磨層2的形狀並無特別限定。形狀可列舉圓盤狀、帶狀等，較佳為圓盤狀。
研磨墊1的大小（直徑）可根據配備研磨墊1的研磨裝置的尺寸等進行決定，例如可設為直徑10 cm～1 m左右。
研磨層2的厚度較佳為0.1 mm～10 mm，更佳為0.3 mm～5 mm。
另外，本發明的研磨墊亦可僅包括研磨層。The structure of the polishing pad of the present invention will be described using FIGS. 1 to 3. As shown in FIG. 1, the
在研磨墊1中，較佳為將研磨層2經由接著層3而接著於緩衝（cushion）層4。接著層3是用於使研磨層2與緩衝層4接著的層，通常包括黏著帶或黏著材。In the
緩衝層4是使研磨層2向被研磨物的抵接更均勻的層。緩衝層4可包括不織布或合成樹脂等具有可撓性的材料。The
研磨墊1藉由配設於緩衝層4的黏著帶等貼附於研磨裝置。研磨墊1在被研磨裝置按壓於被研磨物的狀態下受到旋轉驅動，對被研磨物進行研磨。此時，向研磨墊1與被研磨物之間供給漿料。漿料經由槽或孔供給至研磨面，並被排出。The
＜研磨層＞
構成研磨層2的材料是研磨層2的主要構成成分即樹脂6。而且，視需要，可進而包含中空微小球體5。<Grinding layer>
The material constituting the
當在研磨層2中包含中空微小球體5時，較佳為如圖2中所示，在樹脂6之中分散有中空微小球體5。When the
研磨層2可包含的中空微小球體5例如如圖3中所示，一般具有包含熱塑性樹脂的球殼狀的外殼5a及被外殼包圍的內部空間5b。中空微小球體5是利用熱塑性樹脂的外殼5a包圍著液狀的低沸點烴的形狀。The
針對樹脂6與中空微小球體5的詳細情況，在＜＜研磨墊的製造方法＞＞的項中進行說明。The details of the
＜研磨面＞
本發明的研磨墊1中所具有的研磨層2的研磨面2a可藉由表面加工，視需要設置槽。槽可設置正交的槽（X軸與Y軸）或、穿孔（perforation）加工的槽（藉由穿孔加工形成的槽）、同心圓狀的槽等。關於研磨面的Sa、Spa、Spd將後述。<Polished surface>
The
＜＜研磨墊的製造方法＞＞ 針對本發明的研磨墊的製造方法進行說明。作為研磨墊的材料，只要為可用於研磨的材料，則並無特別限定，例如可列舉使含有胺基甲酸酯鍵的聚異氰酸酯化合物與硬化劑反應而獲得的聚胺基甲酸酯樹脂材料。以下，針對研磨墊的製造方法，以使用含有胺基甲酸酯鍵的聚異氰酸酯化合物與硬化劑而獲得的聚胺基甲酸酯樹脂的研磨墊為例進行說明。<<Manufacturing method of polishing pad>> The method of manufacturing the polishing pad of the present invention will be described. The material of the polishing pad is not particularly limited as long as it can be used for polishing, and examples thereof include a polyurethane resin material obtained by reacting a polyisocyanate compound containing a urethane bond with a hardener. . Hereinafter, a method of manufacturing a polishing pad will be described by taking an example of a polishing pad of a polyurethane resin obtained by using a polyisocyanate compound containing a urethane bond and a hardener.
作為使用了含有胺基甲酸酯鍵的聚異氰酸酯化合物與硬化劑的研磨墊的製造方法，例如可列舉包括如下步驟的製造方法，即：準備步驟，至少準備含有胺基甲酸酯鍵的聚異氰酸酯化合物、硬化劑以及任意選擇性的中空微小球體；混合步驟，至少混合所述含有胺基甲酸酯鍵的聚異氰酸酯化合物、硬化劑、中空微小球體而獲得成形體成形用的混合液；成形體成形步驟，自所述成形體成形用混合液成形聚胺基甲酸酯樹脂成形體；以及研磨層形成步驟，自所述聚胺基甲酸酯樹脂成形體，形成具有用於對被研磨物進行研磨加工的研磨表面的研磨層。As a method of manufacturing a polishing pad using a polyisocyanate compound containing a urethane bond and a hardener, for example, a manufacturing method including the following steps, that is, a preparation step, prepares at least a polymer containing a urethane bond An isocyanate compound, a hardener, and any optional hollow microspheres; in the mixing step, at least the polyisocyanate compound containing a urethane bond, a hardener, and hollow microspheres are mixed to obtain a mixed liquid for molding a molded body; molding A body forming step, forming a polyurethane resin molded body from the mixed liquid for forming the molded body; and an abrasive layer forming step, forming the polyurethane resin molded body from the polyurethane resin molded body The abrasive layer on the surface of the grinding surface.
以下，分準備步驟、混合步驟、成形體成形步驟、研磨層形成步驟來分別進行說明。Hereinafter, the preparation step, the mixing step, the molded body forming step, and the polishing layer forming step will be described respectively.
＜準備步驟＞ 為了製造本發明的研磨墊，作為聚胺基甲酸酯樹脂成形體（硬化樹脂）的原料，準備含有胺基甲酸酯鍵的聚異氰酸酯化合物、硬化劑。而且，出於使樹脂成形體中包含發泡物的目的，準備中空微小球體或水。此處，含有胺基甲酸酯鍵的聚異氰酸酯是用於形成聚胺基甲酸酯樹脂成形體的預聚物。<Preparation steps> In order to manufacture the polishing pad of the present invention, as a raw material of a polyurethane resin molded body (cured resin), a polyisocyanate compound containing a urethane bond and a curing agent are prepared. In addition, for the purpose of containing the foam in the resin molded body, hollow microspheres or water are prepared. Here, the polyisocyanate containing a urethane bond is a prepolymer for forming a molded polyurethane resin.
在準備步驟中，在進而與所述成分一起使用多元醇化合物的情況下，或在不損害本發明的效果的範圍內併用所述以外的成分的情況下，亦準備該些成分。以下，針對各成分進行說明。In the preparation step, when a polyol compound is further used together with the above-mentioned components, or when components other than the above are used together within a range that does not impair the effects of the present invention, these components are also prepared. Hereinafter, each component will be described.
[含有胺基甲酸酯鍵的聚異氰酸酯化合物] 含有胺基甲酸酯鍵的聚異氰酸酯化合物（預聚物）是藉由在通常使用的條件下使下述聚異氰酸酯化合物與多元醇化合物反應而獲得的化合物，在分子內包含胺基甲酸酯鍵與異氰酸酯基。而且，亦可在不損害本發明的效果的範圍內，在含有胺基甲酸酯鍵的聚異氰酸酯化合物中包含其他成分。[Polyisocyanate compound containing urethane bond] A polyisocyanate compound (prepolymer) containing a urethane bond is a compound obtained by reacting the following polyisocyanate compound with a polyol compound under generally used conditions, and contains a urethane in the molecule Bond with isocyanate group. Furthermore, other components may be included in the polyisocyanate compound containing a urethane bond as long as the effect of the present invention is not impaired.
作為含有胺基甲酸酯鍵的聚異氰酸酯化合物，可使用市售者，亦可使用使聚異氰酸酯化合物與多元醇化合物反應而合成者。所述反應並無特別限制，只要使用聚胺基甲酸酯樹脂的製造中公知的方法及條件進行加成聚合反應即可。例如，可利用在加溫至40℃的多元醇化合物中在氮氣體環境下一面攪拌一面添加加溫至50℃的聚異氰酸酯化合物，在30分鐘後升溫至80℃進而在80℃下反應60分鐘的方法來製造。As the polyisocyanate compound containing a urethane bond, a commercially available product may be used, or a compound synthesized by reacting a polyisocyanate compound and a polyol compound may be used. The reaction is not particularly limited, as long as the addition polymerization reaction is performed using methods and conditions known in the production of polyurethane resins. For example, a polyisocyanate compound heated to 50°C can be added to a polyol compound heated to 40°C while stirring in a nitrogen gas atmosphere, and then heated to 80°C after 30 minutes and then reacted at 80°C for 60 minutes. Method.
[聚異氰酸酯化合物] 在本說明書及專利申請範圍中，聚異氰酸酯化合物是指在分子內具有兩個以上的異氰酸酯基的化合物。 作為聚異氰酸酯化合物，只要在分子內具有兩個以上的異氰酸酯基則並無特別限制。例如作為在分子內具有兩個異氰酸酯基的二異氰酸酯化合物，可列舉：間苯二異氰酸酯、對苯二異氰酸酯、2,6-甲苯二異氰酸酯（2,6-TDI）、2,4-甲苯二異氰酸酯（2,4-TDI）、萘-1,4-二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、4,4'-亞甲基-雙(環己基異氰酸酯)（氫化MDI）、3,3'-二甲氧基-4,4'-聯苯二異氰酸酯、3,3'-二甲基二苯基甲烷-4,4'-二異氰酸酯、二甲苯-1,4-二異氰酸酯、4,4'-二苯基丙烷二異氰酸酯、三亞甲基二異氰酸酯、六亞甲基二異氰酸酯、丙烯-1,2-二異氰酸酯、丁烯-1,2-二異氰酸酯、環己烯-1,2-二異氰酸酯、環己烯-1,4-二異氰酸酯、對伸苯基二異硫氰酸酯、二甲苯-1,4-二異硫氰酸酯、次乙基二異硫氰酸酯等。 作為聚異氰酸酯化合物，較佳為二異氰酸酯化合物，其中更佳為2,4-TDI、2,6-TDI、MDI，尤佳為2,4-TDI、2,6-TDI。 該些聚異氰酸酯化合物可單獨使用，亦可組合多個聚異氰酸酯化合物來使用。[Polyisocyanate compound] In the scope of this specification and patent application, the polyisocyanate compound refers to a compound having two or more isocyanate groups in the molecule. The polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule. For example, examples of the diisocyanate compound having two isocyanate groups in the molecule include isophthalic diisocyanate, terephthalic diisocyanate, 2,6-toluene diisocyanate (2,6-TDI), and 2,4-toluene diisocyanate. (2,4-TDI), naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), 4,4'-methylene-bis (cyclohexyl isocyanate) (hydrogenated MDI), 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylene-1,4 -Diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butene-1,2-diisocyanate, cyclohexyl Ene-1,2-diisocyanate, cyclohexene-1,4-diisocyanate, p-phenylene diisothiocyanate, xylene-1,4-diisothiocyanate, ethylidene diisocyanate Thiocyanate, etc. The polyisocyanate compound is preferably a diisocyanate compound, among which 2,4-TDI, 2,6-TDI, and MDI are more preferable, and 2,4-TDI and 2,6-TDI are particularly preferable. These polyisocyanate compounds may be used alone or in combination with a plurality of polyisocyanate compounds.
[作為預聚物的原料的多元醇化合物] 在本說明書及專利申請範圍中，多元醇化合物是指在分子內具有兩個以上的羥基（OH）的化合物。 作為用於作為預聚物的含有胺基甲酸酯鍵的聚異氰酸酯化合物的合成的多元醇化合物，可列舉：乙二醇、二乙二醇（DEG）、丁二醇等二醇化合物、三醇化合物等；聚(氧基四亞甲基)二醇（或聚四亞甲基醚二醇）（PTMG）等聚醚多元醇化合物；乙二醇與己二酸的反應產物或丁二醇與己二醇的反應產物等聚酯多元醇化合物；聚碳酸酯多元醇化合物、聚己內酯多元醇化合物等。而且，亦可使用加成有環氧乙烷的3官能性丙二醇。該些中，較佳為PTMG、或PTMG與DEG的組合。 所述多元醇化合物可單獨使用，亦可組合多個多元醇化合物來使用。[Polyol compound as raw material for prepolymer] In the scope of this specification and patent application, a polyol compound refers to a compound having two or more hydroxyl groups (OH) in the molecule. Examples of the polyol compound used in the synthesis of the polyisocyanate compound containing a urethane bond as a prepolymer include glycol compounds such as ethylene glycol, diethylene glycol (DEG), and butylene glycol. Alcohol compounds, etc.; polyether polyol compounds such as poly(oxytetramethylene) glycol (or polytetramethylene ether glycol) (PTMG); reaction products of ethylene glycol and adipic acid or butanediol Polyester polyol compounds such as reaction products with hexanediol; polycarbonate polyol compounds, polycaprolactone polyol compounds, etc. Furthermore, trifunctional propylene glycol added with ethylene oxide can also be used. Among these, PTMG or a combination of PTMG and DEG is preferred. The polyol compound may be used alone or in combination with a plurality of polyol compounds.
（預聚物的異氰酸酯（NCO）當量） 作為表示預聚物即含有胺基甲酸酯鍵的聚異氰酸酯化合物的特徵的指標，可列舉NCO當量。NCO當量是利用「(聚異氰酸酯化合物的質量份+多元醇化合物的質量份)/[(聚異氰酸酯化合物每1分子中的官能基數×聚異氰酸酯化合物的質量份/聚異氰酸酯化合物的分子量)-(多元醇化合物每1分子中的官能基數×多元醇化合物的質量份/多元醇化合物的分子量)]」求出，是表示每1個NCO基中的PP（預聚物）的分子量的數值。該NCO當量較佳為200～800，更佳為300～700，進一步更佳為400～600。(Isocyanate (NCO) equivalent of prepolymer) As an index indicating the characteristics of a prepolymer, that is, a polyisocyanate compound containing a urethane bond, NCO equivalent is exemplified. The NCO equivalent is based on the use of "(parts by mass of polyisocyanate compound + parts by mass of polyol compound)/[(number of functional groups per molecule of polyisocyanate compound × part by mass of polyisocyanate compound/molecular weight of polyisocyanate compound)-(multicomponent The number of functional groups per molecule of the alcohol compound×mass part of the polyol compound/molecular weight of the polyol compound)]” is a value indicating the molecular weight of PP (prepolymer) per NCO group. The NCO equivalent is preferably 200 to 800, more preferably 300 to 700, and still more preferably 400 to 600.
[硬化劑] 在本發明的研磨墊的製造方法中，在混合步驟中使硬化劑（亦稱為鏈伸長劑）與含有胺基甲酸酯鍵的聚異氰酸酯化合物等混合。藉由加入硬化劑，在其後的成形體成形步驟中，含有胺基甲酸酯鍵的聚異氰酸酯化合物的主鏈末端與硬化劑鍵結而形成聚合物鏈，進行硬化。 作為硬化劑，例如可使用多胺化合物及/或多元醇化合物。[hardener] In the manufacturing method of the polishing pad of the present invention, in the mixing step, a hardener (also referred to as a chain extender) and a polyisocyanate compound containing a urethane bond are mixed. By adding a hardener, in the subsequent forming step of the shaped body, the main chain end of the polyisocyanate compound containing a urethane bond is bonded to the hardener to form a polymer chain, and is hardened. As the hardener, for example, polyamine compounds and/or polyol compounds can be used.
[多胺化合物] 在本說明書及專利申請範圍中，多胺化合物是指在分子內具有兩個以上的胺基的化合物。 作為多胺化合物，可使用脂肪族或芳香族的多胺化合物，特別是二胺化合物，例如可列舉：乙二胺、丙二胺、六亞甲基二胺、異佛爾酮二胺、二環己基甲烷-4,4'-二胺、3,3'-二氯-4,4'-二胺基二苯基甲烷(亞甲基雙-鄰氯苯胺)（以下，簡稱為MOCA）、具有與MOCA同樣的結構的多胺化合物等。而且，多胺化合物可具有羥基，作為此種胺系化合物，例如可列舉2-羥基乙基乙二胺、2-羥基乙基丙二胺、二-2-羥基乙基乙二胺、二-2-羥基乙基丙二胺、2-羥基丙基乙二胺、二-2-羥基丙基乙二胺等。 作為多胺化合物，較佳為二胺化合物，更佳為MOCA、二胺基二苯基甲烷、二胺基二苯基碸，尤佳為MOCA。[Polyamine compound] In this specification and the scope of patent applications, polyamine compounds refer to compounds having two or more amine groups in the molecule. As the polyamine compound, aliphatic or aromatic polyamine compounds can be used, and particularly diamine compounds, for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, diamine Cyclohexyl methane-4,4'-diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (methylenebis-o-chloroaniline) (hereinafter referred to as MOCA), Polyamine compounds etc. having the same structure as MOCA. Moreover, the polyamine compound may have a hydroxyl group, and examples of such an amine compound include 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propane diamine, di-2-hydroxy ethyl ethylene diamine, and di- 2-hydroxyethylpropanediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. The polyamine compound is preferably a diamine compound, more preferably MOCA, diaminodiphenylmethane, and diaminodiphenylsulfone, particularly preferably MOCA.
此處，作為MOCA，例如可列舉潘德克斯（PANDEX）E（迪愛生（DIC）公司製造）、依哈拉秋阿民（IHARACUAMINE MT）（日本組合化學（KUMIAI CHEMICAL）公司製造）等。 多胺化合物可單獨使用，亦可組合多個多胺化合物來使用。Here, as MOCA, for example, PANDEX (made by DIC), IHARACUAMINE MT (made by KUMIAI CHEMICAL) and the like can be cited. The polyamine compound may be used alone or in combination with multiple polyamine compounds.
多胺化合物為了容易與其他成分混合及/或為了提高之後的成形體形成步驟中氣泡徑的均勻性，較佳為視需要在加熱的狀態下在減壓下進行脫泡。作為減壓下的脫泡方法，使用聚胺基甲酸酯樹脂的製造中公知的方法即可，例如可使用真空泵在0.1 MPa以下的真空度下進行脫泡。 在使用固體的化合物作為硬化劑（鏈伸長劑）的情況下，可一面藉由加熱進行熔融，一面在減壓下進行脫泡。In order to easily mix the polyamine compound with other components and/or to improve the uniformity of the bubble diameter in the subsequent molded body forming step, it is preferable to perform degassing under reduced pressure under heating as necessary. As a defoaming method under reduced pressure, a method known in the production of polyurethane resin may be used. For example, a vacuum pump can be used to perform defoaming under a vacuum of 0.1 MPa or less. When a solid compound is used as a hardening agent (chain extender), it can be degassed under reduced pressure while being melted by heating.
[預聚物合成後可使用的多元醇化合物] 而且，在本發明中，亦可獨立於為了形成所述作為預聚物的含有胺基甲酸酯鍵的聚異氰酸酯化合物而使用的多元醇化合物，使用多元醇化合物作為硬化劑。 作為該多元醇化合物，只要為二元醇化合物或三元醇化合物等化合物，則可無特別限制地使用。而且，可與用於形成預聚物的多元醇化合物相同，亦可不同。 作為具體例，可列舉：乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇等低分子量二醇、聚(氧基四亞甲基)二醇、聚乙二醇、聚丙二醇等高分子量多元醇化合物等。 所述多元醇化合物可單獨使用，亦可組合多個多元醇化合物來使用。[Polyol compound that can be used after prepolymer synthesis] Furthermore, in the present invention, a polyol compound may be used as a hardener independently of the polyol compound used to form the urethane bond-containing polyisocyanate compound as a prepolymer. The polyol compound can be used without particular limitation as long as it is a compound such as a diol compound or a triol compound. Moreover, it may be the same as or different from the polyol compound used to form the prepolymer. Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and new Low molecular weight diols such as pentanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, poly(oxytetramethylene) glycol, polyethylene glycol , Polypropylene glycol and other high molecular weight polyol compounds. The polyol compound may be used alone or in combination with a plurality of polyol compounds.
作為硬化劑，可使用多胺化合物，可使用多元醇化合物，亦可使用該些的混合物。As the hardener, a polyamine compound, a polyol compound, or a mixture of these may be used.
（R值） 在本發明的研磨墊的製造方法中，較佳為以使硬化劑中存在的活性氫基（胺基及羥基）相對於作為預聚物的含有胺基甲酸酯鍵的聚異氰酸酯化合物的末端存在的異氰酸酯基的當量比即R值成為0.60～1.40的方式混合各成分。R值更佳為0.70～1.20，進而佳為0.80～1.10。(R value) In the manufacturing method of the polishing pad of the present invention, it is preferable to make the active hydrogen group (amine group and hydroxyl group) present in the hardener relative to the terminal of the polyisocyanate compound containing a urethane bond as a prepolymer Each component is mixed so that the equivalent ratio of the existing isocyanate groups, that is, the R value becomes 0.60 to 1.40. The R value is more preferably 0.70 to 1.20, and further preferably 0.80 to 1.10.
[中空微小球體] 在本發明的研磨墊的製造方法中，可視需要使用中空微小球體或水使聚胺基甲酸酯樹脂成形體內部內包氣泡。 中空微小球體是指具有空隙的微小球體。在中空微小球體中包含球狀、橢圓狀及接近於該些的形狀者。作為示例，可列舉使未發泡的加熱膨脹性微小球狀體加熱膨脹而成者。 作為所述聚合物殼，如日本專利特開昭57-137323號公報等中所揭示般，例如可使用丙烯腈-偏二氯乙烯共聚物、丙烯腈-甲基丙烯酸甲酯共聚物、氯乙烯-乙烯共聚物等熱塑性樹脂。同樣地，作為內包於聚合物殼的低沸點烴，例如可使用異丁烷、戊烷、異戊烷、石油醚等。[Hollow microsphere] In the manufacturing method of the polishing pad of the present invention, hollow microspheres or water may be used to entrap bubbles in the polyurethane resin molded body as necessary. Hollow microspheres refer to microspheres with voids. The hollow microsphere includes spherical, elliptical, and shapes close to those. As an example, a non-foamed heat-expandable microsphere is heated and expanded. As the polymer shell, as disclosed in Japanese Patent Laid-Open No. 57-137323, etc., for example, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-methyl methacrylate copolymer, vinyl chloride can be used -Thermoplastic resins such as ethylene copolymers. Similarly, as the low-boiling-point hydrocarbon encapsulated in the polymer shell, for example, isobutane, pentane, isopentane, petroleum ether, and the like can be used.
中空微小球體亦能夠利用市售品。例如可利用松本微球系列（Matsumoto microsphere series）（松本油脂製藥股份有限公司製造）或埃克斯帕塞爾（Expancel）（阿克蘇諾貝爾（AkzoNobel）公司製造）作為中空微小球體。市售的中空微小球體有已經經加熱膨脹的已膨脹型與尚未經加熱膨脹的未膨脹型。已膨脹型幾乎不受藉由後述的混合步驟產生的反應熱的影響而可實現固定的氣泡徑，另一方面，未膨脹型會因藉由後述的混合步驟產生的反應熱而膨脹。因此在為未膨脹型的情況下，為了控制氣泡徑，例如需要調整將藉由聚合反應而生成的反應熱迅速地冷卻或迅速地促進聚合反應，藉由中空微小球體的周圍存在的樹脂強制性地抑制膨脹等反應條件。Hollow microspheres can also use commercially available products. For example, Matsumoto microsphere series (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd.) or Expancel (manufactured by AkzoNobel) can be used as the hollow microspheres. The commercially available hollow microspheres have an expanded type that has been thermally expanded and an unexpanded type that has not been thermally expanded. The expanded type is hardly affected by the reaction heat generated by the mixing step described below, and a fixed bubble diameter can be achieved. On the other hand, the unexpanded type expands due to the reaction heat generated by the mixing step described later. Therefore, in the case of an unexpanded type, in order to control the bubble diameter, for example, it is necessary to adjust the reaction heat generated by the polymerization reaction to rapidly cool or rapidly promote the polymerization reaction, and the resin existing around the hollow microspheres is mandatory To suppress swelling and other reaction conditions.
作為中空微小球體的平均粒徑，較佳為使用10 μm～150 μm的中空微小球體。已膨脹型的中空微小球體的平均粒徑更佳為15 μm～130 μm，進一步更佳為20 μm～100 μm，進一步更佳為20 μm～60 μm，尤佳為30 μm～50 μm。另外，已膨脹型已經膨脹，因此包含於樹脂前的中空微小球體的平均粒徑與研磨層形成後的中空微小球體的平均氣泡徑變化不大。 而且，已膨脹型只市售平均粒徑為20 μm以上者，因此在欲將樹脂中的氣泡徑設為不足20 μm的情況下，需要使用平均粒徑10 μm～20 μm的未膨脹型的中空微小球體，調整反應條件，以使中空微小球體幾乎不膨脹的方式進行控制。未膨脹型的中空微小球體的平均粒徑較佳為使用10 μm～20 μm，在經過後述的各步驟後，作為分散於研磨層的聚胺基甲酸酯樹脂中的氣泡的平均氣泡徑較佳為10 μm～20 μm，更佳為12 μm～20 μm，更佳為15 μm～20 μm。 另外，使用前的中空微小球體的平均粒徑可藉由雷射繞射式粒度分佈測定裝置（例如思百吉（spectris）（股）製造的粒度分析儀（mastersizer）2000）來進行測定。 而且，研磨墊中的中空微小球體的平均氣泡徑可藉由自雷射顯微鏡的測定圖像進行圖像處理來進行測定。As the average particle diameter of the hollow microspheres, it is preferable to use hollow microspheres of 10 μm to 150 μm. The average particle diameter of the expanded hollow microspheres is more preferably 15 μm to 130 μm, further more preferably 20 μm to 100 μm, even more preferably 20 μm to 60 μm, and particularly preferably 30 μm to 50 μm. In addition, since the expanded type has expanded, the average particle diameter of the hollow microspheres contained before the resin does not change much from the average bubble diameter of the hollow microspheres after the polishing layer is formed. In addition, the expanded type is only commercially available with an average particle size of 20 μm or more. Therefore, when the bubble diameter in the resin is to be less than 20 μm, it is necessary to use an unexpanded type with an average particle size of 10 μm to 20 μm. The hollow microspheres are controlled by adjusting the reaction conditions so that the hollow microspheres hardly expand. The average particle diameter of the unexpanded hollow microspheres is preferably 10 μm to 20 μm. After the steps described later, the average bubble diameter of the bubbles dispersed in the polyurethane resin dispersed in the polishing layer is It is preferably 10 μm to 20 μm, more preferably 12 μm to 20 μm, and still more preferably 15 μm to 20 μm. In addition, the average particle diameter of the hollow microspheres before use can be measured by a laser diffraction particle size distribution measuring device (for example, a particle size analyzer (mastersizer 2000) manufactured by spectris (shares)). Furthermore, the average bubble diameter of the hollow microspheres in the polishing pad can be measured by performing image processing on the measurement image from the laser microscope.
中空微小球體相對於研磨層的材料，較佳為10體積%～60體積%，更佳為15體積%～45體積%。中空微小球體在研磨層因研磨而磨損後，露出至研磨面，影響研磨面的研磨特性。The volume of the hollow microspheres relative to the material of the polishing layer is preferably 10% by volume to 60% by volume, and more preferably 15% by volume to 45% by volume. The hollow microspheres are exposed to the polishing surface after the polishing layer is worn by the polishing, which affects the polishing characteristics of the polishing surface.
中空微小球體以相對於預聚物100質量份，較佳為0.1質量份～10質量份、更佳為1質量份～5質量份、進一步更佳為2質量份～4質量份的方式進行添加。The hollow microspheres are added in such a manner that it is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, and even more preferably 2 to 4 parts by mass relative to 100 parts by mass of the prepolymer. .
＜混合步驟＞ 在混合步驟中，將所述準備步驟中所獲得的、含有胺基甲酸酯鍵的聚異氰酸酯化合物（預聚物）、硬化劑供於混合機內進行攪拌、混合。混合步驟是在加溫為可確保所述各成分的流動性的溫度的狀態下進行。 在混合步驟中，至少將含有胺基甲酸酯鍵的聚異氰酸酯化合物（預聚物）、硬化劑及中空微小球體供給至混合機內進行攪拌、混合。混合順序並無特別限制，較佳為準備混合含有胺基甲酸酯鍵的聚異氰酸酯化合物與中空微小球體而得的混合液、及混合硬化劑及視需要的其他成分而得的混合液，將兩混合液供給至混合器內進行混合攪拌。如此，製備成形體成形用的混合液。混合步驟是在加溫為可確保所述各成分的流動性的溫度的狀態下進行。<Mixing step> In the mixing step, the urethane bond-containing polyisocyanate compound (prepolymer) obtained in the preparation step and the curing agent are stirred and mixed in the mixer. The mixing step is performed in a state of being heated to a temperature that can ensure the fluidity of the components. In the mixing step, at least a polyisocyanate compound (prepolymer) containing a urethane bond, a hardener, and hollow microspheres are supplied into the mixer and stirred and mixed. The mixing order is not particularly limited. It is preferable to prepare a mixed liquid obtained by mixing a polyisocyanate compound containing a urethane bond and hollow microspheres, a mixed liquid obtained by mixing a hardener and other components as needed, and The two mixed liquids are supplied to the mixer for mixing and stirring. In this way, a mixed liquid for forming a molded body is prepared. The mixing step is performed in a state of being heated to a temperature that can ensure the fluidity of the components.
＜成形體成形步驟＞ 在成形體成形步驟中，進行藉由在將所述混合步驟中製備的成形體成形用混合液流入至預熱至30℃～100℃的模具框內使其一次硬化後，在100℃～150℃左右進行10分鐘～5小時左右的加熱，使其二次硬化而硬化的聚胺基甲酸酯樹脂（聚胺基甲酸酯樹脂成形體）的成形。此時，預聚物、硬化劑反應而形成聚胺基甲酸酯樹脂，藉此該混合液硬化。<Molding step> In the molded body forming step, the mixed liquid for forming the molded body prepared in the mixing step is flowed into a mold frame preheated to 30°C to 100°C to be hardened once, and then at 100°C to 150 Polyurethane resin (polyurethane resin molded body) molded by heating at about 10 minutes to about 5 hours at a temperature of about 2 to 5 hours for secondary curing. At this time, the prepolymer and the hardener react to form a polyurethane resin, whereby the mixed liquid is hardened.
＜研磨層形成步驟＞ 將藉由成形體成形步驟而獲得的聚胺基甲酸酯樹脂成形體切片（slice）為片材狀而形成聚胺基甲酸酯樹脂片材。藉由被切片，而可在片材表面設置開孔。此時，為了形成耐磨耗性優異且不易阻塞的研磨層表面的開孔，亦可在30℃～150℃下進行1小時～24小時左右的老化（Aging）。<Step of forming polishing layer> The polyurethane resin molded body obtained by the molding step is sliced into a sheet to form a polyurethane resin sheet. By being sliced, openings can be provided on the surface of the sheet. At this time, in order to form an opening on the surface of the polishing layer that is excellent in wear resistance and hardly clogged, aging (Aging) may be performed at 30°C to 150°C for about 1 to 24 hours.
關於如此獲得的具有聚胺基甲酸酯樹脂片材的研磨層，其後在研磨層的研磨面相反側的面上貼附雙面膠帶，切割為規定形狀，較佳為圓板狀，而作為本發明的研磨墊而完成。雙面膠帶並無特別限制，可自該技術領域中公知的雙面膠帶之中任意地選擇使用。Regarding the polishing layer having the polyurethane resin sheet thus obtained, a double-sided tape is then attached to the surface opposite to the polishing surface of the polishing layer, and cut into a predetermined shape, preferably a disc shape, and It is completed as the polishing pad of the present invention. The double-sided tape is not particularly limited, and can be arbitrarily selected from double-sided tapes known in the technical field.
而且，本發明的研磨墊可為僅包含研磨層的單層結構，亦可為包含在研磨層的研磨面相反側的面上貼合其他層（下層、支撐層、在圖1中為緩衝層）的多層。其他層的特性並無特別限定，較佳為在研磨層的相反側的面上貼合較研磨層柔軟（A硬度或D硬度小）的層。若貼合較研磨層柔軟的層，則研磨平坦性進一步提高。另一方面，若在研磨層的相反側的面上貼合較研磨層硬（A硬度或D硬度大）的層，則研磨率進一步提高。Furthermore, the polishing pad of the present invention may have a single-layer structure including only the polishing layer, or may include another layer (the lower layer, the supporting layer, and the buffer layer in FIG. 1) bonded to the surface opposite to the polishing surface of the polishing layer ) Of multiple layers. The characteristics of the other layers are not particularly limited, and it is preferable that a layer softer than the polishing layer (smaller A hardness or D hardness) is bonded to the surface on the opposite side of the polishing layer. If a layer softer than the polishing layer is bonded, the polishing flatness is further improved. On the other hand, if a layer harder than the polishing layer (large A hardness or D hardness) is bonded to the surface on the opposite side of the polishing layer, the polishing rate is further improved.
在具有多層結構的情況下，只要使用雙面膠帶或接著劑等（視需要進行加壓）將多層彼此接著/固定即可。此時所使用的雙面膠帶或接著劑並無特別限制，可自該技術領域中公知的雙面膠帶或接著劑之中任意地選擇使用。In the case of having a multi-layer structure, it is only necessary to use double-sided tape, an adhesive, or the like (pressurizing if necessary) to bond/fix the multiple layers to each other. The double-sided tape or adhesive used at this time is not particularly limited, and can be arbitrarily selected from double-sided tapes or adhesives known in the technical field.
進而，本發明的研磨墊可視需要對研磨層的表面及/或背面進行研削處理，或在表面實施槽加工或壓花加工，可將基材及/或黏著層貼合於研磨層，亦可包括光透過部。 槽加工及壓花加工的形狀並無特別限制，例如可列舉格子型、同心圓型、放射型等形狀。Furthermore, the polishing pad of the present invention can grind the surface and/or back of the polishing layer as needed, or perform groove processing or embossing on the surface, and the substrate and/or the adhesive layer can be attached to the polishing layer, or Including the light transmission part. The shape of the groove processing and the embossing processing is not particularly limited, and examples thereof include lattice shapes, concentric circles, and radial shapes.
[表面處理] 本發明的研磨墊的研磨面可實施物理性或化學性處理。在不進行表面處理的情況下，只要可將研磨面製成規定的範圍的Sa、Spc（若必要則有Spd），仍可縮短磨合時間且可減少瑕疵。但是，若進行了表面處理則容易達成規定的Sa、Spc，因此較佳為實施表面處理。 而且，以往表面粗糙度中，將僅測定接觸式的方法特定的線方向的Ra用作指標，在表面處理的方向（旋轉方向等）偏向特定方向的情況下難以測定正確的表面狀態。本發明藉由利用光學式的方法測定表面粗糙度，而能夠測定考慮到方向性的正確的表面狀態。[Surface treatment] The polishing surface of the polishing pad of the present invention may be subjected to physical or chemical treatment. Without surface treatment, as long as the polished surface can be made into Sa and Spc (spd if necessary) within a specified range, the running-in time can be shortened and defects can be reduced. However, if surface treatment is performed, it is easy to achieve predetermined Sa and Spc, so it is preferable to perform surface treatment. Moreover, in the conventional surface roughness, Ra is measured only in the line direction specified by the contact method as an index, and it is difficult to measure the accurate surface state when the direction of surface treatment (rotation direction, etc.) is deviated to a specific direction. In the present invention, by measuring the surface roughness by an optical method, it is possible to measure the correct surface state in consideration of the directionality.
在本發明的研磨墊中，作為用於達成規定的範圍的Sa及Spc（若必要則有Spd）的一個表面處理的方法，可列舉拋光處理。因此，本發明的研磨墊較佳為經拋光處理。此處，拋光處理是使用砂紙將研磨面一定程度上粗糙化處理後，將布、皮、橡膠等的拋光件一面旋轉，一面按壓至研磨面，對表面進行處理的方法。In the polishing pad of the present invention, as one surface treatment method for achieving Sa and Spc (if necessary, Spd if necessary) in a predetermined range, polishing treatment may be mentioned. Therefore, the polishing pad of the present invention is preferably polished. Here, the polishing treatment is a method of roughening the polished surface to a certain extent using sandpaper, and then pressing the polishing material such as cloth, leather, rubber, etc., while pressing it against the polished surface to treat the surface.
本發明中用於拋光處理的砂紙的粒度號並無特別限定，較佳為#120～#600。這是因為藉由使用此種砂紙，容易調整為恰當的Sa及Spc。The particle size number of the sandpaper used for polishing in the present invention is not particularly limited, but is preferably #120 to #600. This is because by using such sandpaper, it is easy to adjust to the appropriate Sa and Spc.
本發明中，拋光處理中砂紙的紙圓周速度並無特別限定，較佳為300 m/min～1500 m/min。當成為小於300 m/min的紙圓周速度時，切削力變低而有無法充分將表面粗糙化之虞。而且，當成為大於1500 m/min的紙圓周速度時，切削力變得過大而難以實現規定的範圍的Sa、Spc（若必要則有Spd）。In the present invention, the paper peripheral speed of the sandpaper during polishing is not particularly limited, but it is preferably 300 m/min to 1500 m/min. When the paper circumferential speed is less than 300 m/min, the cutting force becomes low and the surface may not be sufficiently roughened. Moreover, when the paper circumferential speed is greater than 1500 m/min, the cutting force becomes too large, and it is difficult to achieve Sa and Spc in a predetermined range (if necessary, Spd).
本發明中，拋光處理中按壓拋光件時的平台速度並無特別限定，較佳為0.1 m/min～20 m/min。 在本發明中，較佳為將所述紙圓周速度與平台速度之比（紙圓周速度/平台速度）設為50～750。藉由使所述平台速度相對於所述紙速度而言充分慢，可一面將切削力設為較佳的範圍一面抑制剪切力，從而能夠實現規定的範圍的Sa、Spc（若必要則有Spd）。當使紙圓周速度/平台速度小於50時，產生剪切力，發生不期望的撕裂，峰頂點成為尖起的形狀，或峰頂點的數量增加，難以實現規定範圍的Sa、Spc、Spd。而且，當使紙圓周速度/平台速度大於750時，切削力變得過大，難以實現規定範圍的Sa、Spc、Spd。In the present invention, the platform speed when pressing the polishing member during polishing is not particularly limited, but is preferably 0.1 m/min to 20 m/min. In the present invention, the ratio of the paper peripheral speed to the platform speed (paper peripheral speed/platform speed) is preferably set to 50 to 750. By making the platform speed sufficiently slower than the paper speed, the cutting force can be suppressed while setting the cutting force to a preferable range, thereby enabling the Sa and Spc within a prescribed range (if necessary Spd). When the paper peripheral speed/platform speed is less than 50, shear force is generated, undesirable tearing occurs, the peak apex becomes a sharp shape, or the number of peak apexes increases, and it is difficult to realize Sa, Spc, and Spd within a prescribed range. Moreover, when the paper peripheral speed/table speed is greater than 750, the cutting force becomes too large, and it is difficult to realize Sa, Spc, and Spd within a predetermined range.
本發明的研磨墊包括無表面處理或者若必要則藉由進行此種拋光處理等表面處理，而具有規定的範圍的Sa、Spc、Spd的研磨層。The polishing pad of the present invention includes a polishing layer having Sa, Spc, and Spd in a predetermined range without surface treatment or by performing such surface treatment such as polishing treatment if necessary.
在本發明中，研磨層的研磨面的Sa為3 μm～10 μm。若處於此範圍，則起到可縮短磨合時間的效果。Sa的下限較佳為3 μm以上，更佳為4 μm以上。另一方面，Sa的上限較佳為10 μm以下，更佳為8 μm以下。In the present invention, Sa of the polishing surface of the polishing layer is 3 μm to 10 μm. If it is within this range, it has the effect of shortening the running-in time. The lower limit of Sa is preferably 3 μm or more, and more preferably 4 μm or more. On the other hand, the upper limit of Sa is preferably 10 μm or less, and more preferably 8 μm or less.
在本發明中，研磨層的研磨面的Spc為200～600（1/mm）。若處於此範圍，則起到減少刮痕的效果。Spc的下限較佳為200（1/mm）以上，更佳為300（1/mm）以上。另一方面，Spc的上限較佳為600（1/mm）以下，更佳為500（1/mm）以下。In the present invention, the Spc of the polishing surface of the polishing layer is 200 to 600 (1/mm). If it is in this range, the effect of reducing scratches is achieved. The lower limit of Spc is preferably 200 (1/mm) or more, and more preferably 300 (1/mm) or more. On the other hand, the upper limit of Spc is preferably 600 (1/mm) or less, and more preferably 500 (1/mm) or less.
在本發明中，研磨層的研磨面的Spd較佳為2000～6000（1/mm2 ）。若處於此範圍，則起到減少刮痕的效果，因此較佳。Spd的下限較佳為2000（1/mm2 ）以上，更佳為3000（1/mm2 ）以上。另一方面，Spd的上限較佳為6000（1/mm2 ）以下，更佳為5000（1/mm2 ）以下。In the present invention, Spd of the polishing surface of the polishing layer is preferably 2000 to 6000 (1/mm 2 ). If it is within this range, the effect of reducing scratches is obtained, which is preferable. The lower limit of Spd is preferably 2000 (1/mm 2 ) or more, and more preferably 3000 (1/mm 2 ) or more. On the other hand, the upper limit of Spd is preferably 6000 (1/mm 2 ) or less, and more preferably 5000 (1/mm 2 ) or less.
使用本發明的研磨墊時，將研磨墊以研磨層的研磨面與被研磨物相向的方式安裝於研磨機的研磨平台。而且，一面供給研磨漿料一面使研磨平台旋轉，對被研磨物的加工表面進行研磨。 [實施例]When using the polishing pad of the present invention, the polishing pad is attached to the polishing platform of the polishing machine so that the polishing surface of the polishing layer faces the object to be polished. Then, while supplying the polishing slurry, the polishing platform is rotated to polish the processed surface of the object to be polished. [Example]
以下，針對本發明，使用實施例詳細地進行說明，但本發明並不限定於實施例。Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the examples.
（表面狀態的測定） Sa、Spc及Spd是使用雷射顯微鏡進行測定。(Determination of surface condition) Sa, Spc and Spd are measured using a laser microscope.
（瑕疵的評價） 將研磨墊經由具有丙烯酸系接著劑的雙面膠帶設置於研磨裝置的規定位置，對Cu膜基板在下述條件下實施研磨加工。 （研磨條件） 研磨機：F-REX300（荏原製作所公司製造） 盤（Disk）：A188（3M公司製造） 轉速：（平台）70 rpm､（頂環（top ring））71 rpm 研磨壓力：3.5 psi 研磨劑溫度：20℃ 研磨劑噴出量：200 ml/min 研磨劑：PLANERLITE7000（福吉米公司（Fujimi Corporation）公司製造） 被研磨物：Cu膜基板 研磨時間：60秒 墊磨合（pad break）：35 N 10分鐘 修整（conditioning）：Ex-situ、35 N、4次掃描（scan） 對於所述研磨加工後的被研磨物第10枚以後至第50枚為止，針對被研磨面的大於155 nm的直線狀的研磨傷（刮痕）及點狀的研磨傷（微小刮痕），利用eDR5210（科磊（KLA-Tencor）公司製造）的ReviewSEM目視進行刮痕數量的確認。(Evaluation of defects) The polishing pad was installed at a predetermined position of the polishing apparatus via a double-sided tape with an acrylic adhesive, and the Cu film substrate was polished under the following conditions. (Grinding conditions) Grinding machine: F-REX300 (made by Ebara Manufacturing Co., Ltd.) Disk (Disk): A188 (manufactured by 3M) Speed: (platform) 70 rpm (top ring (top ring) 71 rpm Grinding pressure: 3.5 psi Abrasive temperature: 20℃ Abrasive spray volume: 200 ml/min Abrasive: PLANERLITE7000 (manufactured by Fujimi Corporation) Object to be polished: Cu film substrate Grinding time: 60 seconds Pad break: 35 N 10 minutes Conditioning: Ex-situ, 35 N, 4 scans For the 10th to the 50th to-be-polished objects after the polishing process, for linear polishing scratches (scratches) and point-like polishing scratches (micro scratches) greater than 155 nm on the polished surface, The number of scratches was confirmed visually using ReviewDR of eDR5210 (manufactured by KLA-Tencor).
（參考研磨墊的製造） 在使2,4-甲苯二異氰酸酯（TDI）、聚(氧基四亞甲基)二醇（PTMG）及二乙二醇（DEG）反應而成的NCO當量460的異氰酸酯基末端胺基甲酸酯預聚物100份中，添加混合殼部分包含丙烯腈-偏二氯乙烯共聚物，殼內內包有異丁烷氣體的未膨脹型的中空體3份，獲得混合液。將所獲得的混合液裝入至第一液槽中，進行保溫。其次，獨立於第一液，作為硬化劑，添加混合MOCA 25.5份及聚丙二醇（PPG）8.5份，在第二液槽內進行保溫。將第一液槽、第二液槽各自的液體以使表示硬化劑中存在的胺基及羥基相對於預聚物中的末端異氰酸酯基的當量比的R值成為0.90的方式自具有兩個注入口的混合機各自的注入口注入至所述混合機。將注入的兩種液體一面混合攪拌一面注入至預熱的成形機的金屬模具，之後，進行合模，加熱30分鐘，進行一次硬化。將一次硬化的成形物脫模後，利用烘箱在130℃下進行2小時的二次硬化，獲得胺基甲酸酯成形物。在將所獲得的胺基甲酸酯成形物放置冷卻至25℃後，再次利用烘箱在120℃下加熱5小時後切片為1.3 mm的厚度，獲得研磨墊。所獲得的研磨墊的平均氣泡徑為15 μm。(Refer to the manufacture of polishing pads) Isocyanate group-terminated amino acid with NCO equivalent of 460 obtained by reacting 2,4-toluene diisocyanate (TDI), poly(oxytetramethylene) glycol (PTMG) and diethylene glycol (DEG) To 100 parts of the ester prepolymer, 3 parts of an unexpanded hollow body containing an acrylonitrile-vinylidene chloride copolymer and an isobutane gas in the shell were added to obtain a mixed liquid. The obtained mixed liquid was put into the first liquid tank and kept warm. Next, independent of the first liquid, as a hardener, 25.5 parts of MOCA and 8.5 parts of polypropylene glycol (PPG) were added and mixed, and heat preservation was performed in the second liquid tank. The liquids in the first liquid tank and the second liquid tank each have two values so that the R value representing the equivalent ratio of the amine group and the hydroxyl group present in the hardener to the terminal isocyanate group in the prepolymer becomes 0.90. Each inlet of the inlet mixer is injected into the mixer. The two injected liquids were mixed and stirred while being injected into the metal mold of the preheated molding machine, after which, the mold was closed, heated for 30 minutes, and hardened once. After demolding the primary-cured molded product, secondary curing was performed in an oven at 130° C. for 2 hours to obtain a urethane molded product. After the obtained urethane molded article was left to cool to 25°C, it was heated again at 120°C for 5 hours in an oven and sliced to a thickness of 1.3 mm to obtain a polishing pad. The average bubble diameter of the obtained polishing pad was 15 μm.
（參考研磨墊的打磨處理） 針對所獲得的研磨墊，不進行拋光處理，而進行打磨處理。作為打磨處理，是使用打磨機（dresser），對研磨墊的表面進行若干量的研磨的處理，作為研磨機，使用荏原製作所股份有限公司製造的商品名「F-REX300」，將平台轉速設定為80 rpm，將打磨壓力設定為20 N，將漿料噴出量設定為1.5 L/分，作為漿料使用純水進行10分鐘打磨（dressing）。將所獲得的參考研磨墊的研磨面的SEM照片示於圖4。(Refer to the polishing process of the polishing pad) The obtained polishing pad is not polished but polished. As the polishing process, a dresser is used to polish the surface of the polishing pad by a certain amount. As the polishing machine, the trade name "F-REX300" manufactured by Ebara Manufacturing Co., Ltd. is used, and the platform rotation speed is set to At 80 rpm, the grinding pressure was set to 20 N, the amount of slurry ejection was set to 1.5 L/min, and pure water was used for slurry dressing for 10 minutes. The SEM photograph of the obtained polishing surface of the reference polishing pad is shown in FIG. 4.
使用進行了打磨處理的參考研磨墊，而且，使用試驗用被研磨樣本，進行研磨。研磨速度不充分，所以交替進行打磨處理與試驗樣本的預備研磨，在打磨處理第25次時成為目標研磨速度。而且，在使用了參考研磨墊時，確認到刮痕數為3個，微小刮痕數為25個，研磨傷（刮痕）少。The reference polishing pad subjected to the polishing process was used, and the test sample to be polished was used for polishing. The polishing speed is insufficient, so the polishing process and the preliminary polishing of the test sample are alternately performed, which becomes the target polishing rate at the 25th polishing process. Furthermore, when a reference polishing pad was used, it was confirmed that the number of scratches was 3, the number of minute scratches was 25, and there were few abrasive scratches (scratches).
此時的參考研磨墊的研磨面的Sa為4.7，Spc為490，Spd為4800。At this time, Sa of the polishing surface of the reference polishing pad was 4.7, Spc was 490, and Spd was 4800.
（實施例1） 針對藉由與參考研磨墊相同的製造方法而獲得的研磨墊，不進行打磨處理，使用粒度號#240的紙，在紙圓周速度（500 m/ml）、平台速度（1 m/分）的條件下以餘量成為50 μm的方式進行拋光處理，藉此獲得研磨墊A。對研磨墊A（拋光處理後）的研磨面的表面的Sa、Spc、Spd分別測定四次取平均值。各自的結果是，Sa為4.3，Spc為420，Spd為3600。將所獲得的實施例1的研磨墊的研磨面的SEM照片示於圖5。 使用此研磨墊A進行研磨試驗，結果即便不進行打磨處理，亦有充分的研磨率。即，可縮短磨合的時間。進而，確認到刮痕數為2個，微小刮痕數為18個，研磨傷（刮痕）少。(Example 1) For the polishing pad obtained by the same manufacturing method as the reference polishing pad, no sanding treatment is used, and paper with a particle size of #240 is used. At a paper peripheral speed (500 m/ml) and a platform speed (1 m/min) Under the conditions, the polishing process is performed so that the remaining amount becomes 50 μm, whereby the polishing pad A is obtained. Sa, Spc, and Spd on the surface of the polishing surface of the polishing pad A (after polishing treatment) were measured four times and averaged. The respective results are that Sa is 4.3, Spc is 420, and Spd is 3600. The obtained SEM photograph of the polishing surface of the polishing pad of Example 1 is shown in FIG. 5. Using this polishing pad A, a polishing test was performed, and as a result, even if no polishing treatment was performed, a sufficient polishing rate was obtained. That is, the running-in time can be shortened. Furthermore, it was confirmed that the number of scratches was 2, the number of minute scratches was 18, and there were few abrasive scratches (scratches).
（實施例2） 針對藉由與參考研磨墊相同的製造方法而獲得的研磨墊，不進行打磨處理，使用粒度號#180的紙，在紙圓周速度（500 m/ml）、平台速度（1 m/分）的條件下進行拋光處理，藉此獲得研磨墊B。對研磨墊B（拋光處理後）的研磨面的表面的Sa、Spc、Spd分別測定四次取平均值。各自的結果是，Sa為5.4，Spc為480，Spd為4500。將所獲得的實施例2的研磨墊的研磨面的SEM照片示於圖6。 使用此研磨墊B進行研磨試驗，結果即便不進行打磨處理，亦有充分的研磨率。即，可縮短磨合的時間。進而，確認到刮痕數為4個，微小刮痕數為26個，研磨傷（刮痕）少。(Example 2) For the polishing pad obtained by the same manufacturing method as the reference polishing pad, no sanding treatment is used, and paper with a particle size of #180 is used. At a paper peripheral speed (500 m/ml) and a platform speed (1 m/min) The polishing process is performed under the conditions, whereby the polishing pad B is obtained. Sa, Spc, and Spd on the surface of the polishing surface of polishing pad B (after polishing treatment) were measured four times and averaged. The respective results are that Sa is 5.4, Spc is 480, and Spd is 4500. The obtained SEM photograph of the polishing surface of the polishing pad of Example 2 is shown in FIG. 6. Using this polishing pad B, a polishing test was performed, and as a result, even if no polishing treatment was performed, a sufficient polishing rate was obtained. That is, the running-in time can be shortened. Furthermore, it was confirmed that the number of scratches was 4, the number of minute scratches was 26, and there were few abrasive scratches (scratches).
（比較例1） 針對藉由與參考研磨墊相同的製造方法而獲得的研磨墊，使用粒度號#120的紙，在紙圓周速度（1000 m/ml）、平台速度（1 m/分）的條件下進行拋光處理，藉此獲得研磨墊C。對研磨墊C（拋光處理後）的研磨面的表面的Sa、Spc、Spd分別測定四次取平均值。各自的結果是，Sa為6.3，Spc為800，Spd為8200。將所獲得的比較例1的研磨墊的研磨面的SEM照片示於圖7。 使用此研磨墊C進行研磨試驗，結果雖可縮短磨合的時間，但確認到刮痕數為9個，微小刮痕數為42個，與實施例相比研磨傷（刮痕）多。(Comparative example 1) For the polishing pad obtained by the same manufacturing method as the reference polishing pad, use paper with a particle size of #120, and perform polishing treatment under the conditions of the paper peripheral speed (1000 m/ml) and the platform speed (1 m/min) , Thereby obtaining the polishing pad C. Sa, Spc, and Spd on the surface of the polishing surface of the polishing pad C (after polishing treatment) were measured four times and averaged. The respective results are that Sa is 6.3, Spc is 800, and Spd is 8200. The obtained SEM photograph of the polishing surface of the polishing pad of Comparative Example 1 is shown in FIG. 7. The polishing test was performed using this polishing pad C. As a result, it was possible to shorten the running-in time, but it was confirmed that the number of scratches was 9 and the number of minute scratches was 42, which was more abrasive scratches (scratches) than in Examples.
將比較例1的研磨墊C與具有充分的研磨率，瑕疵亦少的參考研磨墊進行比較，Ra的值幾乎相等，但就瑕疵的觀點而言，不可謂為優異的研磨墊。認為是因為Sa、Spc、Spd等值未處於規定的範圍內。 另一方面，認為研磨墊A及研磨墊B可縮短磨合的時間，且瑕疵少是因為具有與進行了打磨處理的參考研磨墊相等的Ra、Sa、Spc，進而Spd亦相等。Comparing the polishing pad C of Comparative Example 1 with a reference polishing pad having a sufficient polishing rate and few defects, the value of Ra is almost equal, but from the viewpoint of defects, it cannot be said to be an excellent polishing pad. It is considered that the values such as Sa, Spc, and Spd are not within the prescribed range. On the other hand, it is considered that the polishing pad A and the polishing pad B can shorten the running-in time, and the fewer defects are because they have the same Ra, Sa, and Spc as the reference polishing pad that has been polished, and the Spd is also equal.
1:研磨墊
2:研磨層
2a:研磨面
3:接著層
4:緩衝層
5:中空微小球體
5a:外殼
5b:內部空間
6:樹脂1: Grinding pad
2: Grinding
圖1是本發明的研磨墊的立體圖。 圖2是本發明的研磨墊的剖面圖。 圖3是本發明的研磨墊中所含的中空微小球體的剖面圖。 圖4是參考研磨墊的研磨面的掃描式電子顯微鏡（scanning electron microscope，SEM）照片。 圖5是實施例1的研磨墊的研磨面的SEM照片。 圖6是實施例2的研磨墊的研磨面的SEM照片。 圖7是比較例1的研磨墊的研磨面的SEM照片。FIG. 1 is a perspective view of the polishing pad of the present invention. 2 is a cross-sectional view of the polishing pad of the present invention. 3 is a cross-sectional view of hollow microspheres contained in the polishing pad of the present invention. 4 is a photograph of a scanning electron microscope (SEM) referring to the polishing surface of the polishing pad. 5 is an SEM photograph of the polishing surface of the polishing pad of Example 1. FIG. 6 is an SEM photograph of the polishing surface of the polishing pad of Example 2. FIG. 7 is an SEM photograph of the polishing surface of the polishing pad of Comparative Example 1. FIG.
1:研磨墊 1: Grinding pad
2:研磨層 2: Grinding layer
2a:研磨面 2a: Polished surface
3:接著層 3: then layer
4:緩衝層 4: buffer layer
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