TW202304651A - Polishing pad and method for manufacturing polishing pad - Google Patents

Abstract

This polishing pad has a polishing layer that comprises an isocyanate-terminated prepolymer and a polyurethane resin foam derived from a curing agent, wherein: the distance between hard segments in the polishing layer as measured by small-angle X-ray scattering is 9.5 nm or less; or the ratio (NC80/CC80) of the content proportion by weight (NC80) of an amorphous phase in the polishing layer as measured by pulse NMR at 80 DEG C to the content proportion by weight (CC80) of a crystalline phase in the polishing layer as measured by pulse NMR at 80 DEG C is 2.6-3.1, and the ratio (NC40/CC40) of the content proportion by weight (NC80) of an amorphous phase in the polishing layer as measured by pulse NMR at 40 DEG C to the content proportion by weight (CC80) of a crystalline phase in the polishing layer as measured by pulse NMR at 40 DEG C is 0.5-0.9.

Description

研磨墊及研磨墊的製造方法Polishing pad and manufacturing method of polishing pad

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適宜地用於光學材料、半導體晶圓、半導體元件、硬碟用基板等的研磨中的研磨墊。The invention relates to a grinding pad. Specifically, the present invention relates to a polishing pad that can be suitably used for polishing optical materials, semiconductor wafers, semiconductor elements, substrates for hard disks, and the like.

作為用於使光學材料、半導體晶圓、半導體元件、硬碟用基板的表面平坦化的研磨法，通常使用化學機械研磨（chemical mechanical polishing，CMP）法。As a polishing method for flattening the surface of an optical material, a semiconductor wafer, a semiconductor element, or a hard disk substrate, a chemical mechanical polishing (CMP) method is generally used.

使用圖1對CMP法進行說明。如圖1般，實施CMP法的研磨裝置1中包括研磨墊3，所述研磨墊3與被保持於保持壓盤16上的被研磨物8抵接，且包括作為進行研磨的層的研磨層4與支撐研磨層4的緩衝層6。研磨墊3於被研磨物8被按壓的狀態下受到旋轉驅動，從而對被研磨物8進行研磨。此時，向研磨墊3與被研磨物8之間供給漿料9。漿料9是水與各種化學成分或硬質的微細研磨粒的混合物（分散液），藉由其中的化學成分或研磨粒於流動的同時與被研磨物8進行相對運動，而增大研磨效果。漿料9經由槽或孔被供給至研磨面而被排出。The CMP method will be described using FIG. 1 . As shown in FIG. 1 , a polishing apparatus 1 for implementing the CMP method includes a polishing pad 3 that contacts an object to be polished 8 held on a holding platen 16 and includes a polishing layer as a layer for polishing. 4 and the buffer layer 6 supporting the abrasive layer 4. The polishing pad 3 is driven to rotate while the object to be polished 8 is pressed, thereby polishing the object to be polished 8 . At this time, the slurry 9 is supplied between the polishing pad 3 and the object to be polished 8 . The slurry 9 is a mixture (dispersion liquid) of water and various chemical components or hard fine abrasive particles, and the chemical components or abrasive particles move relative to the object to be ground 8 while flowing, thereby increasing the grinding effect. Slurry 9 is supplied to the polishing surface through the grooves or holes and discharged.

且說，於半導體元件的研磨中，通常利用使用硬質聚胺基甲酸酯材料作為研磨層4的研磨墊，所述硬質聚胺基甲酸酯材料是使包含異氰酸酯成分（甲苯二異氰酸酯（Toluene Diisocyanate，TDI）等）及高分子量多元醇（聚氧基四亞甲基二醇（Polyoxy tetramethylene Glycol，PTMG）等）的預聚物、與二胺系硬化劑（4,4'-亞甲基雙(2-氯苯胺)（3,3'-二氯-4,4'-二胺基二苯基甲烷（3,3'-Dichloro-4,4'-Diaminodiphenylmethane，MOCA））等）進行反應而獲得。預聚物中所含的高分子量多元醇形成胺基甲酸酯的軟鏈段，且自先前起便經常使用顯示出其操作容易性或適度的橡膠彈性的PTMG作為高分子量多元醇。And say, in the grinding of semiconductor element, generally utilize the polishing pad that uses hard polyurethane material as grinding layer 4, and described hard polyurethane material is made to contain isocyanate component (Toluene Diisocyanate (Toluene Diisocyanate) , TDI), etc.) and prepolymers of high-molecular-weight polyols (Polyoxy tetramethylene Glycol, PTMG, etc.), and diamine-based hardeners (4,4'-methylenebis (2-chloroaniline) (3,3'-dichloro-4,4'-diaminodiphenylmethane (3,3'-Dichloro-4,4'-Diaminodiphenylmethane, MOCA)) etc.) get. The high-molecular-weight polyol contained in the prepolymer forms a soft segment of urethane, and PTMG, which exhibits its ease of handling or moderate rubber elasticity, has been often used as the high-molecular-weight polyol heretofore.

然而，近年來，隨著半導體元件的配線的微細化，於先前的研磨墊中，有時階差消除性能或瑕疵（defect）性能不充分，正研究使用PTMG以外的物質作為高分子量多元醇。However, in recent years, with the miniaturization of the wiring of semiconductor elements, conventional polishing pads may have insufficient level difference elimination performance or defect performance, and use of substances other than PTMG as high molecular weight polyols has been studied.

作為研究了所述般的課題的文獻，專利文獻1中揭示有一種研磨墊，其中藉由使用聚丙二醇（Polypropylene Glycol，PPG）作為預聚物的高分子量多元醇，而階差消除性能高、刮痕少。As a document that has studied such a subject, Patent Document 1 discloses a polishing pad in which a high-molecular-weight polyol using polypropylene glycol (PPG) as a prepolymer has high level difference elimination performance, Less scratches.

另外，專利文獻2中揭示有一種研磨墊，其中藉由使用PPG及PTMG的混合物作為預聚物的高分子量多元醇，而減低了缺陷率。 [現有技術文獻] [專利文獻] In addition, Patent Document 2 discloses a polishing pad in which a defect rate is reduced by using a mixture of PPG and PTMG as a prepolymer high molecular weight polyol. [Prior art literature] [Patent Document]

[專利文獻1]日本專利特開2020-157415號公報 [專利文獻2]日本專利特開2011-040737號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2020-157415 [Patent Document 2] Japanese Patent Laid-Open No. 2011-040737

[發明所欲解決之課題][Problem to be Solved by the Invention]

但是，專利文獻1中記載的研磨墊存在研磨層的耐磨耗性差、研磨墊的壽命短的問題點。另外，專利文獻2中記載的研磨墊存在階差消除性能或瑕疵性能不充分的問題點。However, the polishing pad described in Patent Document 1 has problems in that the abrasion resistance of the polishing layer is poor and the life of the polishing pad is short. In addition, the polishing pad described in Patent Document 2 has a problem of insufficient level difference eliminating performance or flaw performance.

本發明是鑒於所述問題點而成，目的在於提供一種階差消除性能或瑕疵性能優異、進而耐磨耗性優異的研磨墊。 [解決課題之手段] The present invention is made in view of the above-mentioned problems, and an object of the present invention is to provide a polishing pad having excellent level difference eliminating performance and flaw performance, and furthermore, excellent wear resistance. [Means to solve the problem]

本發明者進行了努力研究，結果發現，於研磨墊所具有的研磨層中使用的材料中，在為硬鏈段間的距離為特定長度般的結構的情況下，成為階差消除性能或瑕疵性能優異、進而耐磨耗性優異的研磨墊，從而達成了本發明。 另外，本發明者等人對研磨層的結晶相、中間相、非晶相的比例進行了研究，發現於80℃下的結晶相與非晶相的比例為特定範圍內、且40℃下的結晶相與非晶相的比例處於特定範圍內時，可解決所述課題，從而達成了本發明。 即，本發明包含以下內容。 [1] 一種研磨墊，具有包含聚胺基甲酸酯樹脂發泡體的研磨層，所述聚胺基甲酸酯樹脂發泡體源自異氰酸酯末端預聚物及硬化劑，所述研磨墊中， 藉由X射線小角散射法測定的所述研磨層中的硬鏈段間的距離為9.5 nm以下。 [2] 如[1]所述的研磨墊，其中所述異氰酸酯末端預聚物包含源自聚異氰酸酯化合物的構成單元、與源自高分子量多元醇的構成單元， 所述源自高分子量多元醇的構成單元至少包含聚丙二醇構成單元、與聚酯二醇構成單元。 [3] 如[2]所述的研磨墊，其中相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元小於60重量%。 [4] 如[2]所述的研磨墊，其中用於形成所述聚酯二醇構成單元的聚酯二醇為600～2500的數量平均分子量。 [5] 如[1]所述的研磨墊，其中所述聚胺基甲酸酯樹脂發泡體的平均氣泡徑為5 μm以上且小於20 μm。 [6] 如[1]所述的研磨墊，其中所述異氰酸酯末端預聚物的NCO當量為500～600。 [7] 如[1]所述的研磨墊，其中藉由X射線小角散射法測定的所述研磨層中的硬鏈段間的距離為3.0 nm～9.5 nm。 [8] 一種研磨墊的製造方法，製造具有包含聚胺基甲酸酯樹脂發泡體的研磨層的研磨墊，所述製造方法包括： 將異氰酸酯末端預聚物與硬化劑混合並進行反應，從而獲得所述聚胺基甲酸酯樹脂發泡體的步驟；以及 將所述聚胺基甲酸酯樹脂發泡體成形並製成研磨層的形狀的步驟，並且 藉由X射線小角散射法測定的所述研磨層中的硬鏈段間的距離為9.5 nm以下。 [9] 如[8]所述的研磨墊的製造方法，其中於將異氰酸酯末端預聚物與硬化劑混合時，亦使未膨脹氣球共存。 [10] 一種研磨墊，具有包含聚胺基甲酸酯樹脂發泡體的研磨層，所述聚胺基甲酸酯樹脂發泡體源自異氰酸酯末端預聚物及硬化劑，所述研磨墊中， 藉由脈衝核磁共振（Nuclear Magnetic Resonance，NMR）法於80℃下所測定的所述研磨層中的非晶相的含有重量比例（NC80）相對於藉由脈衝NMR法於80℃下所測定的所述研磨層中的結晶相的含有重量比例（CC80）的比（NC80/CC80）為2.6～3.1， 藉由脈衝NMR法於40℃下所測定的所述研磨層中的非晶相的含有重量比例（NC40）相對於藉由脈衝NMR法於40℃下所測定的所述研磨層中的結晶相的含有重量比例（CC40）的比（NC40/CC40）為0.5～0.9。 [11] 如[10]所述的研磨墊，其中由下述式（1）獲得的數值大於1.9且小於2.2， [數式1] （NC80/CC80）-（NC40/CC40）  ･･･（1）。 [12] 如[10]所述的研磨墊，其中所述CC80為19.0重量%～22.0重量%。 [13] 如[10]所述的研磨墊，其中所述NC40為22.0重量%～27.0重量%。 [14] 如[10]所述的研磨墊，其中所述異氰酸酯末端預聚物包含源自聚異氰酸酯化合物的構成單元、與源自高分子量多元醇的構成單元， 所述源自高分子量多元醇的構成單元至少包含聚丙二醇構成單元、與聚酯二醇構成單元。 [15] 如[14]所述的研磨墊，其中相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元小於60重量%。 [16] 如[14]或[15]所述的研磨墊，其中用於形成所述聚酯二醇構成單元的聚酯二醇為600～2500的數量平均分子量。 [17] 如[10]所述的研磨墊，其中所述異氰酸酯末端預聚物的NCO當量為500～600。 [18] 一種研磨墊的製造方法，製造具有包含聚胺基甲酸酯樹脂發泡體的研磨層的研磨墊，所述製造方法包括： 將異氰酸酯末端預聚物與硬化劑混合並進行反應，從而獲得所述聚胺基甲酸酯樹脂發泡體的步驟；以及 將所述聚胺基甲酸酯樹脂發泡體成形並製成研磨層的形狀的步驟，並且 藉由脈衝NMR法於80℃下所測定的所述研磨層中的非晶相的含有重量比例（NC80）相對於藉由脈衝NMR法於80℃下所測定的所述研磨層中的結晶相的含有重量比例（CC80）的比（NC80/CC80）為2.6～3.1， 藉由脈衝NMR法於40℃下所測定的所述研磨層中的非晶相的含有重量比例（NC40）相對於在40℃下所測定的所述研磨層中的結晶相的含有重量比例（CC40）的比（NC40/CC40）為0.5～0.9。 [19] 一種研磨墊，具有包含聚胺基甲酸酯樹脂發泡體的研磨層，所述聚胺基甲酸酯樹脂發泡體源自異氰酸酯末端預聚物及硬化劑，所述研磨墊中， 所述異氰酸酯末端預聚物包含源自聚異氰酸酯化合物的構成單元、與源自高分子量多元醇的構成單元， 所述源自高分子量多元醇的構成單元至少包含聚丙二醇構成單元、與聚酯二醇構成單元， 相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元小於60重量%。 [20] 如[19]所述的研磨墊，其中相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元為30重量%～50重量%。 [21] 如[19]或[20]所述的研磨墊，其中所述聚酯二醇構成單元源自具有600～2500的數量平均分子量的聚酯二醇。 [22] 一種製造方法，製造具有包含聚胺基甲酸酯樹脂發泡體的研磨層的研磨墊，所述製造方法包括： 使聚異氰酸酯化合物、與至少包含聚丙二醇及聚酯二醇的高分子量多元醇進行反應，從而獲得異氰酸酯末端預聚物的步驟； 使所述異氰酸酯末端預聚物與硬化劑進行反應，從而獲得所述聚胺基甲酸酯樹脂發泡體的步驟；以及 將所述聚胺基甲酸酯樹脂發泡體成形並製成研磨層的形狀的步驟，並且 相對於所述高分子量多元醇總量，所述聚丙二醇小於60重量%。 [發明的效果] As a result of intensive research by the present inventors, it was found that, in the case of a structure in which the distance between hard segments is a specific length in the material used for the polishing layer of the polishing pad, it becomes the level difference elimination performance or the defect. The present invention has been achieved by providing a polishing pad with excellent performance and further excellent wear resistance. In addition, the inventors of the present invention have studied the ratio of the crystalline phase, the intermediate phase, and the amorphous phase of the polishing layer, and found that the ratio of the crystalline phase to the amorphous phase at 80°C is within a specific range and at 40°C When the ratio of the crystal phase and the amorphous phase is within a specific range, the above-mentioned problems can be solved, and the present invention has been achieved. That is, the present invention includes the following. [1] A polishing pad having a polishing layer comprising a polyurethane resin foam derived from an isocyanate-terminated prepolymer and a hardener, the polishing pad middle, The distance between the hard segments in the polishing layer measured by X-ray small-angle scattering method is 9.5 nm or less. [2] The polishing pad according to [1], wherein the isocyanate-terminated prepolymer includes a structural unit derived from a polyisocyanate compound and a structural unit derived from a high-molecular-weight polyol, The structural unit derived from the high molecular weight polyol includes at least a polypropylene glycol structural unit and a polyester diol structural unit. [3] The polishing pad according to [2], wherein the polypropylene glycol constituting unit is less than 60% by weight relative to the constituting unit derived from a high molecular weight polyol. [4] The polishing pad according to [2], wherein the polyester diol used to form the polyester diol constituent unit has a number average molecular weight of 600 to 2,500. [5] The polishing pad according to [1], wherein the polyurethane resin foam has an average cell diameter of 5 μm or more and less than 20 μm. [6] The polishing pad according to [1], wherein the NCO equivalent of the isocyanate-terminated prepolymer is 500 to 600. [7] The polishing pad according to [1], wherein the distance between hard segments in the polishing layer measured by X-ray small-angle scattering method is 3.0 nm to 9.5 nm. [8] A manufacturing method of a polishing pad, manufacturing a polishing pad having a polishing layer comprising a polyurethane resin foam, the manufacturing method comprising: a step of mixing and reacting an isocyanate-terminated prepolymer and a hardener to obtain the polyurethane resin foam; and a step of shaping the polyurethane resin foam into the shape of an abrasive layer, and The distance between the hard segments in the polishing layer measured by X-ray small-angle scattering method is 9.5 nm or less. [9] The method for producing a polishing pad according to [8], wherein when the isocyanate-terminated prepolymer and the curing agent are mixed, unexpanded balloons are also allowed to coexist. [10] A polishing pad having a polishing layer comprising a polyurethane resin foam derived from an isocyanate-terminated prepolymer and a hardener, the polishing pad middle, The content ratio (NC80) of the amorphous phase in the polishing layer measured at 80°C by the pulse nuclear magnetic resonance (NMR) method is compared to the content ratio (NC80) of the amorphous phase measured at 80°C by the pulse NMR method. The ratio (NC80/CC80) of the content ratio (CC80) of the crystal phase in the polishing layer is 2.6 to 3.1, The content ratio (NC40) of the amorphous phase in the polishing layer measured at 40°C by the pulse NMR method relative to the crystalline phase in the polishing layer measured at 40°C by the pulse NMR method The ratio (NC40/CC40) of the contained weight ratio (CC40) is 0.5-0.9. [11] The polishing pad as described in [10], wherein the value obtained by the following formula (1) is more than 1.9 and less than 2.2, [Formula 1] (NC80/CC80)-(NC40/CC40) ･･･(1). [12] The polishing pad according to [10], wherein the CC80 is 19.0% by weight to 22.0% by weight. [13] The polishing pad according to [10], wherein the NC40 is 22.0% by weight to 27.0% by weight. [14] The polishing pad according to [10], wherein the isocyanate-terminated prepolymer comprises a structural unit derived from a polyisocyanate compound and a structural unit derived from a high molecular weight polyol, The structural unit derived from the high molecular weight polyol includes at least a polypropylene glycol structural unit and a polyester diol structural unit. [15] The polishing pad according to [14], wherein the polypropylene glycol constituting unit is less than 60% by weight relative to the constituting unit derived from a high molecular weight polyol. [16] The polishing pad as described in [14] or [15], wherein the polyester diol used to form the polyester diol constituent unit has a number average molecular weight of 600 to 2,500. [17] The polishing pad according to [10], wherein the NCO equivalent weight of the isocyanate-terminated prepolymer is 500 to 600. [18] A method of manufacturing a polishing pad, manufacturing a polishing pad having a polishing layer comprising a polyurethane resin foam, the manufacturing method comprising: a step of mixing and reacting an isocyanate-terminated prepolymer and a hardener to obtain the polyurethane resin foam; and a step of shaping the polyurethane resin foam into the shape of an abrasive layer, and Content ratio (NC80) of the amorphous phase in the polishing layer measured at 80°C by the pulse NMR method relative to the crystalline phase in the polishing layer measured at 80°C by the pulse NMR method The ratio (NC80/CC80) of the contained weight ratio (CC80) is 2.6 to 3.1, The weight ratio (NC40) of the amorphous phase in the polishing layer measured at 40°C by the pulse NMR method relative to the weight ratio of the crystalline phase in the polishing layer measured at 40°C ( CC40) ratio (NC40/CC40) is 0.5 to 0.9. [19] A polishing pad having a polishing layer comprising a polyurethane resin foam derived from an isocyanate-terminated prepolymer and a hardener, the polishing pad middle, The isocyanate-terminated prepolymer includes a structural unit derived from a polyisocyanate compound and a structural unit derived from a high-molecular-weight polyol, The structural units derived from high molecular weight polyols include at least polypropylene glycol structural units and polyester diol structural units, The polypropylene glycol constituent unit is less than 60% by weight relative to the constituent unit derived from the high molecular weight polyol. [20] The polishing pad according to [19], wherein the polypropylene glycol structural unit is 30% by weight to 50% by weight relative to the structural unit derived from a high molecular weight polyol. [21] The polishing pad as described in [19] or [20], wherein the polyester diol constituent unit is derived from a polyester diol having a number average molecular weight of 600 to 2,500. [22] A manufacturing method for manufacturing a polishing pad having a polishing layer comprising a polyurethane resin foam, the manufacturing method comprising: A step of reacting polyisocyanate compounds with high molecular weight polyols comprising at least polypropylene glycol and polyester diol to obtain an isocyanate-terminated prepolymer; reacting the isocyanate-terminated prepolymer with a hardener to obtain the polyurethane resin foam; and a step of shaping the polyurethane resin foam into the shape of an abrasive layer, and The polypropylene glycol is less than 60% by weight relative to the total amount of the high molecular weight polyol. [Effect of the invention]

本發明的研磨墊所具有的研磨層具有特定長度的硬鏈段間的距離，藉此可提供一種階差消除性能或瑕疵性能優異、進而耐磨耗性優異的研磨墊。The polishing layer of the polishing pad of the present invention has a distance between hard segments of a specific length, thereby providing a polishing pad excellent in level difference elimination performance or flaw performance, and further excellent in abrasion resistance.

以下，對用於實施發明的形態進行說明，但本發明不限定於用於實施發明的形態。Hereinafter, the form for carrying out the invention will be described, but the present invention is not limited to the form for carrying out the invention.

＜＜研磨墊＞＞ 使用圖2的（a）說明研磨墊3的結構。如圖2的（a）般，研磨墊3包括研磨層4及緩衝層6。研磨墊3的形狀較佳為圓盤狀，但並無特別限定，另外，大小（直徑）亦可根據包括研磨墊3的研磨裝置1的尺寸等適宜決定，例如可設為直徑10 cm～2 m左右。 再者，本發明的研磨墊3較佳為如圖2的（a）所示般使研磨層4經由接著層7接著於緩衝層6。 研磨墊3藉由配設於緩衝層6的雙面膠帶等貼附於研磨裝置1的研磨壓盤10。研磨墊3藉由研磨裝置1於按壓被研磨物8的狀態下受到旋轉驅動，對被研磨物8進行研磨（參照圖1）。 ＜＜Grinding Pad＞＞ The structure of the polishing pad 3 will be described using FIG. 2( a ). As shown in FIG. 2( a ), the polishing pad 3 includes a polishing layer 4 and a buffer layer 6 . The shape of the polishing pad 3 is preferably disc-shaped, but it is not particularly limited. In addition, the size (diameter) can also be suitably determined according to the size of the grinding device 1 including the polishing pad 3, for example, it can be set as a diameter of 10 cm to 2 cm. about m. Furthermore, in the polishing pad 3 of the present invention, the polishing layer 4 is preferably bonded to the buffer layer 6 via the bonding layer 7 as shown in FIG. 2( a ). The polishing pad 3 is attached to the polishing platen 10 of the polishing device 1 through a double-sided tape or the like disposed on the buffer layer 6 . The polishing pad 3 is driven to rotate while pressing the object 8 to be polished by the polishing device 1 , and polishes the object 8 to be polished (see FIG. 1 ).

＜研磨層＞ （結構） 研磨墊3包括作為用於對被研磨物8進行研磨的層的研磨層4。構成研磨層4的材料為特定聚胺基甲酸酯樹脂。 研磨層4的大小（直徑）與研磨墊3相同，可設為直徑10 cm～2 m左右，研磨層4的厚度通常可設為1 mm～5 mm左右。 研磨層4與研磨裝置1的研磨壓盤10一同旋轉，於其上一邊使漿料9流動，一邊使漿料9中所含的化學成分或研磨粒與被研磨物8一起相對運動，藉此對被研磨物8進行研磨。 研磨層4中分散有中空微小球體4A。於分散有中空微小球體4A的情況下，在研磨層4被磨耗時，中空微小球體4A露出至研磨面並於研磨面產生微小的空隙，該微小的空隙保持漿料，藉此可進一步進行被研磨物8的研磨。 ＜Grinding layer＞ (structure) The polishing pad 3 includes a polishing layer 4 as a layer for polishing an object 8 to be polished. The material constituting the abrasive layer 4 is a specific polyurethane resin. The size (diameter) of the polishing layer 4 is the same as that of the polishing pad 3, and can be set to about 10 cm to 2 m in diameter, and the thickness of the polishing layer 4 can usually be set to about 1 mm to 5 mm. The grinding layer 4 rotates together with the grinding platen 10 of the grinding device 1, on which the slurry 9 flows, and the chemical components or abrasive particles contained in the slurry 9 move relatively with the object to be ground 8, thereby The object to be ground 8 is ground. Hollow microspheres 4A are dispersed in the grinding layer 4 . In the case where the hollow microspheres 4A are dispersed, when the grinding layer 4 is worn, the hollow microspheres 4A are exposed to the grinding surface and produce tiny voids on the grinding surface, and the tiny voids hold the slurry, thereby enabling further grinding Grinding of grind 8.

研磨層4是藉由如下方式而形成：對將異氰酸酯末端預聚物、硬化劑（鏈伸長劑）、根據需要的中空微小球體4A混合而成的混合液進行澆注並使其硬化，獲得聚胺基甲酸酯樹脂發泡體，對該發泡體進行切片。即，研磨層4經乾式成型。The polishing layer 4 is formed by pouring and hardening a mixed liquid obtained by mixing an isocyanate-terminated prepolymer, a hardener (chain extender), and hollow microspheres 4A if necessary, to obtain a polyamine A urethane resin foam is sliced into slices. That is, the abrasive layer 4 is dry formed.

（硬鏈段間的距離） 於本發明的一態樣中，構成研磨層4的材料藉由X射線小角散射法測定的硬鏈段間的距離為9.5 nm以下。若硬鏈段間的距離為9.5 nm以下，則包括該研磨層的研磨墊具有優異的階差消除性能、優異的瑕疵性能及優異的耐磨耗性。 硬鏈段間的距離較佳為3.0 nm～9.5 nm，更佳為4.0 nm～9.0 nm。 (distance between hard segments) In one aspect of the present invention, the distance between the hard segments of the material constituting the polishing layer 4 measured by X-ray small-angle scattering method is 9.5 nm or less. If the distance between the hard segments is 9.5 nm or less, the polishing pad including the polishing layer has excellent step elimination performance, excellent flaw performance, and excellent wear resistance. The distance between the hard segments is preferably from 3.0 nm to 9.5 nm, more preferably from 4.0 nm to 9.0 nm.

硬鏈段間的距離是藉由X射線小角散射法測定。此處，所謂X射線小角散射法，是藉由對試樣入射X射線，並利用檢測器獲得散射的X射線的方法，可根據散射的角度，非破壞地獲得測定對象的尺寸、形狀、結構相關性等資料。 若對聚胺基甲酸酯樹脂發泡體的研磨層4利用X射線小角散射法進行測定，則可獲得圖3般的曲線。 The distance between hard segments is determined by X-ray small-angle scattering method. Here, the so-called X-ray small-angle scattering method is a method in which X-rays are incident on a sample and scattered X-rays are obtained by a detector, and the size, shape, and structure of the measurement object can be obtained non-destructively according to the scattering angle. related information, etc. When the polishing layer 4 of the polyurethane resin foam is measured by the X-ray small-angle scattering method, a curve like that shown in FIG. 3 can be obtained.

再者，本說明書中，所謂硬鏈段，是指由構成研磨層4的聚胺基甲酸酯樹脂中的藉由異氰酸酯與硬化劑的反應而形成的胺基甲酸酯鍵或脲鍵構成的部分。 通常，於利用X射線小角散射法進行測定的情況下，並不直接使用所獲得的資料的強度（Intensity），而是利用使用以下式子修正後的強度進行研究。於本發明中，亦藉由該計算進行修正。 修正後的強度=（對象樣品的強度/對象樣品的透過率）-（空氣的強度/空氣的透過率） In addition, in this specification, the term "hard segment" refers to the urethane bond or urea bond formed by the reaction between isocyanate and hardener in the polyurethane resin constituting the polishing layer 4. part. Usually, when measuring by the X-ray small-angle scattering method, the intensity (Intensity) of the obtained data is not directly used, but the intensity corrected using the following formula is used for research. In the present invention, correction is also performed by this calculation. Corrected intensity = (intensity of target sample / transmittance of target sample) - (intensity of air / transmittance of air)

硬鏈段間的距離於圖3中所包圍的部分中，由為極大值時的Q的值來算出。即，硬鏈段間的距離可根據距離=2π/Q來求出。因此，若Q的值小，則硬鏈段彼此的距離大。The distance between the hard segments was calculated from the value of Q at the maximum value in the portion enclosed in FIG. 3 . That is, the distance between hard segments can be obtained by distance=2π/Q. Therefore, when the value of Q is small, the distance between the hard segments is large.

使用圖4進行說明。於圖4的曲線中，使用透過率等進行了修正。著眼於該圖4的平坦部分的峰值最高的部位，其X軸對應於硬鏈段間的距離。若如此獲得的硬鏈段間的距離為9.5 nm以下，則包括該研磨層的研磨墊具有優異的階差消除性能、優異的瑕疵性能及優異的耐磨耗性。Description will be made using FIG. 4 . In the graph of FIG. 4 , correction was performed using transmittance or the like. Focusing on the highest peak in the flat portion of FIG. 4 , the X-axis corresponds to the distance between hard segments. If the distance between the hard segments thus obtained is 9.5 nm or less, the polishing pad including the polishing layer has excellent step elimination performance, excellent flaw performance, and excellent wear resistance.

自此開始，進而以容易求出極大值的方式進行轉換。利用以下方法進行圖表再描繪。 （再描繪方法） （1）由所獲得的曲線中強度不斷下降的部分導出切線。例如，根據圖3的測定結果，由Q為0.1～0.2附近的強度導出切線。 （2）根據所述（1）中導出的切線的Q值（X）求出強度，計算與拐點附近的修正後的強度的差。例如，根據圖3的測定結果，Q於0.3～1.2處有拐點，因此求出將Q代入至切線的式子而獲得的強度。其後，自修正後的強度減去藉由切線的式子而獲得的強度來求出差。 （3）根據所述（2）中求出的差，製成強度差的圖表（正態分佈）。 （4）將正態分佈的峰值（圖5中所示的圖表的峰值）推測為硬鏈段間距離。 From there, further conversions are performed so that the maximum value can be easily obtained. Graph redrawing is performed by the following method. (redrawing method) (1) A tangent is derived from the portion of the obtained curve where the intensity decreases. For example, based on the measurement results in FIG. 3 , the tangent line is derived from the intensity where Q is around 0.1 to 0.2. (2) The intensity is obtained from the Q value (X) of the tangent line derived in (1) above, and the difference with the corrected intensity near the inflection point is calculated. For example, from the measurement results in FIG. 3 , Q has an inflection point at 0.3 to 1.2, so the strength obtained by substituting Q into the equation of the tangent is obtained. Thereafter, the intensity obtained by the tangent equation is subtracted from the corrected intensity to obtain a difference. (3) Based on the difference obtained in (2) above, a graph (normal distribution) of intensity difference is prepared. (4) Infer the peak of the normal distribution (the peak of the graph shown in Figure 5) as the hard intersegment distance.

再者，於強度差的圖表的傾斜平緩的情況下，存在硬鏈段的大小參差不齊的傾向（硬鏈段的大小產生偏差的傾向），於強度差的圖表的傾斜陡峭的情況下，存在相同大小的硬鏈段多的傾向（硬鏈段的大小一致的傾向）。Furthermore, when the inclination of the graph of strength difference is gentle, there is a tendency for the size of the hard segment to be uneven (the tendency for the size of the hard segment to vary), and when the inclination of the graph of strength difference is steep, There is a tendency that there are many hard segments of the same size (the hard segments tend to be uniform in size).

如已經說明般，若硬鏈段間的距離為9.5 nm以下，則可獲得良好的特性，該硬鏈段間的距離可藉由變更研磨層4的材料或變更製造方法來調整。 例如，於作為研磨層4的材料的高分子量多元醇是使用聚丙二醇與聚酯二醇兩者而獲得的情況下，藉由改變聚丙二醇及聚酯二醇的比例，而硬鏈段間的距離發生變化。即，藉由變更聚丙二醇及聚酯二醇的比例，可調整硬鏈段間的距離。 As already explained, good properties can be obtained if the distance between the hard segments is 9.5 nm or less, and the distance between the hard segments can be adjusted by changing the material of the polishing layer 4 or changing the manufacturing method. For example, when the high-molecular-weight polyol used as the material of the abrasive layer 4 is obtained by using both polypropylene glycol and polyester glycol, by changing the ratio of polypropylene glycol and polyester glycol, the hard segment The distance changes. That is, by changing the ratio of polypropylene glycol and polyester glycol, the distance between hard segments can be adjusted.

（結晶相、中間相、非晶相） 於本發明的另一態樣中，包含聚胺基甲酸酯樹脂發泡體的研磨層4的特徵在於：藉由脈衝NMR法於80℃下所測定的所述研磨層中的非晶相的含有重量比例（NC80）相對於藉由脈衝NMR法於80℃下所測定的研磨層中的結晶相的含有重量比例（CC80）的比（NC80/CC80）為2.6～3.1，且藉由脈衝NMR法於40℃下所測定的研磨層中的非晶相的含有重量比例（NC40）相對於藉由脈衝NMR法於40℃下所測定的研磨層中的結晶相的含有重量比例（CC40）的比（NC40/CC40）為0.5～0.9。 (crystalline phase, mesophase, amorphous phase) In another aspect of the present invention, the abrasive layer 4 comprising polyurethane resin foam is characterized by the amorphous phase in the abrasive layer measured at 80° C. by a pulsed NMR method. The ratio (NC80/CC80) of the weight ratio (NC80) to the weight ratio (CC80) of the crystalline phase in the polishing layer measured at 80°C by the pulse NMR method is 2.6 to 3.1, and the pulse The weight ratio of the amorphous phase in the polishing layer measured at 40°C by NMR method (NC40) to the weight ratio of the crystalline phase in the polishing layer measured at 40°C by the pulse NMR method (CC40) The ratio (NC40/CC40) is 0.5 to 0.9.

研磨通常是於40℃左右進行，但隨著研磨的進行，研磨墊3的溫度有時會因摩擦而上升至80℃左右。因此，80℃下的非晶相與結晶相的比例重要。於NC80/CC80超過3.1的情況下，由於非晶相的比例相對於結晶相的比例多，因此耐磨耗性有時惡化，另外，於小於2.6的情況下，由於非晶相的比例相對於結晶相的比例少，因此階差消除性能或瑕疵性能有時惡化。NC80/CC80的下限較佳為2.6以上，更佳為2.7以上。NC80/CC80的上限較佳為3.1以下，更佳為3.0以下。 進而，40℃下的非晶相與結晶相的比例亦重要。其原因在於：若40℃下的非晶相與結晶相的比例為特定範圍以外，則瑕疵性能、階差消除性能及耐磨耗性惡化。於40℃下的非晶相的含有重量比例（NC40）相對於結晶相的比（NC40/CC40）超過0.9的情況下，由於非晶相的比例相對於結晶相的比例過多，因此耐磨耗性有時惡化，若小於0.5，則由於非晶相的比例相對於結晶相的比例過少，因此階差消除性能或瑕疵性能有時惡化。NC40/CC40的下限較佳為0.5以上，更佳為0.6以上。NC40/CC40的上限較佳為0.9以下，更佳為0.8以下。 Polishing is usually performed at about 40° C., but as the polishing progresses, the temperature of the polishing pad 3 may rise to about 80° C. due to friction. Therefore, the ratio of the amorphous phase to the crystalline phase at 80°C is important. When NC80/CC80 exceeds 3.1, since the ratio of the amorphous phase to the ratio of the crystalline phase is large, the wear resistance may deteriorate. In addition, when it is less than 2.6, the ratio of the amorphous phase to the Since the ratio of the crystalline phase is small, the level difference elimination performance and flaw performance may deteriorate. The lower limit of NC80/CC80 is preferably at least 2.6, more preferably at least 2.7. The upper limit of NC80/CC80 is preferably at most 3.1, more preferably at most 3.0. Furthermore, the ratio of the amorphous phase to the crystalline phase at 40° C. is also important. The reason for this is that if the ratio of the amorphous phase to the crystalline phase at 40° C. is out of a specific range, the flaw performance, the level difference elimination performance, and the wear resistance will deteriorate. When the weight ratio of the amorphous phase (NC40) to the ratio of the crystalline phase (NC40/CC40) at 40°C exceeds 0.9, the ratio of the amorphous phase to the ratio of the crystalline phase is too high, so wear resistance When the ratio is less than 0.5, the ratio of the amorphous phase to the ratio of the crystalline phase is too small, so the level difference elimination performance or the flaw performance may be deteriorated. The lower limit of NC40/CC40 is preferably at least 0.5, more preferably at least 0.6. The upper limit of NC40/CC40 is preferably at most 0.9, more preferably at most 0.8.

進而，研磨層4較佳為由下述式（1）獲得的數值大於1.9且小於2.2。 [數式2] （NC80/CC80）-（NC40/CC40）  ･･･（1） Furthermore, the polishing layer 4 preferably has a value obtained by the following formula (1) greater than 1.9 and less than 2.2. [Formula 2] (NC80/CC80)-(NC40/CC40) ･･･(1)

所述式（1）是指研磨中的相對於研磨墊的溫度變化的非晶相與結晶相的平衡。於該值為1.9以下的情況下，階差消除性能或瑕疵性能有時惡化，若為2.2以上，則耐磨耗性有時惡化。The above formula (1) refers to the balance of the amorphous phase and the crystalline phase with respect to the temperature change of the polishing pad during polishing. When this value is 1.9 or less, the level difference eliminating performance or flaw performance may deteriorate, and when it is 2.2 or more, abrasion resistance may deteriorate.

由所述式（1）獲得的值的下限較佳為1.95以上，更佳為2.00以上。由所述式（1）獲得的值的上限較佳為2.15以下，更佳為2.10以下。The lower limit of the value obtained by the formula (1) is preferably 1.95 or more, more preferably 2.00 or more. The upper limit of the value obtained by the formula (1) is preferably at most 2.15, more preferably at most 2.10.

進而，相對於研磨層整體的重量，研磨層4的40℃下的非晶相（NC40）的比例較佳為22.0重量%～27.0重量%。若NC40為22.0重量%～27.0重量%，則由於具有軟鏈段為一定量的非晶相的量，因此顯示出優異的階差消除性能、耐磨耗性。 研磨層4的80℃下的結晶相（CC80）較佳為19.0重量%～22.0重量%。若CC80為19.0重量%～22.0重量%，則研磨墊成為合適的硬度，瑕疵性能或階差消除性能提高，因此較佳。 Furthermore, the ratio of the amorphous phase (NC40) at 40° C. in the polishing layer 4 is preferably 22.0% by weight to 27.0% by weight relative to the weight of the entire polishing layer. When NC40 is 22.0% by weight to 27.0% by weight, since there is an amount of an amorphous phase in which the soft segment is a certain amount, excellent step elimination performance and wear resistance are exhibited. The crystal phase (CC80) at 80° C. of the polishing layer 4 is preferably 19.0% by weight to 22.0% by weight. When CC80 is 19.0 weight% - 22.0 weight%, since a polishing pad will become suitable hardness, and a flaw performance or step elimination performance will improve, it is preferable.

另外，於本發明中，研磨層4的結晶相、中間相、非晶相的比例是藉由利用脈衝NMR進行的測定而獲得。於脈衝NMR測定中，按照自旋-自旋弛豫時間長短的順序，將聚胺基甲酸酯樹脂發泡體分為短相（S相）、中相（M相）及長相（L相）此三種成分，求出各相的含有重量比例。再者，關於S相、M相、及L相的含有比例，例如，主要為結晶相時在脈衝NMR測定中觀測到成為S相，主要為非晶相（amorphous phase）時觀測到成為L相，主要為中間相時在脈衝NMR測定中觀測到成為M相。另外，主要為硬鏈段部分時在脈衝NMR測定中觀測到成為S相，主要為軟鏈段部分時觀測到成為L相。 再者，所述自旋-自旋弛豫時間例如可藉由使用日本電子（JEOL）製造的「JNM-MU25」實施利用固體回波（Solid Echo）法進行的測定等來求出。 In addition, in the present invention, the proportions of the crystal phase, mesophase, and amorphous phase of the polishing layer 4 are obtained by measurement by pulse NMR. In the pulse NMR measurement, according to the order of spin-spin relaxation time, the polyurethane resin foam is divided into short phase (S phase), medium phase (M phase) and long phase (L phase). ) of these three components, find the weight ratio of each phase. In addition, regarding the content ratio of S phase, M phase, and L phase, for example, when it is mainly a crystalline phase, it is observed to be an S phase in pulse NMR measurement, and when it is mainly an amorphous phase (amorphous phase), it is observed to be an L phase. , and when it is mainly a mesophase, it is observed as an M phase in pulse NMR measurement. In addition, when it is mainly a hard segment, it is observed to be an S phase in pulse NMR measurement, and when it is mainly a soft segment, it is observed to be an L phase. Note that, the spin-spin relaxation time can be obtained, for example, by performing measurement by a solid echo method using "JNM-MU25" manufactured by JEOL.

（中空微小球體） 本發明的研磨墊中的研磨層4中可含有的中空微小球體4A可於研磨層4的研磨面或研磨層4的剖面中作為中空體來確認到，該中空體通常具有2 μm～200 μm的開口徑（中空微小球體4A的直徑）。作為平均氣泡徑，較佳為5 μm以上且小於20 μm。中空微小球體4A的形狀可列舉球狀、橢圓狀及與該些形狀接近的形狀。 (hollow tiny spheres) The hollow microspheres 4A that can be contained in the polishing layer 4 in the polishing pad of the present invention can be confirmed as hollow bodies in the polishing surface of the polishing layer 4 or in the cross section of the polishing layer 4, and the hollow bodies usually have a diameter of 2 μm to 200 μm. The opening diameter (the diameter of the hollow microsphere 4A). The average cell diameter is preferably not less than 5 μm and less than 20 μm. The shape of the hollow microsphere 4A includes a spherical shape, an elliptical shape, and shapes close to these shapes.

中空微小球體4A可使用市售的氣球，可列舉已膨脹型者、及未膨脹者。未膨脹者是加熱膨脹性微小球狀體，可於製造過程中加熱膨脹而製成規定大小的氣泡。於本發明中，可根據需要適宜使用。As the hollow microsphere 4A, commercially available balloons can be used, and examples thereof include inflated and non-inflated balloons. The unexpanded ones are heat-expandable tiny spheroids, which can be heated and expanded during the manufacturing process to form bubbles of a specified size. In this invention, it can use suitably as needed.

（槽加工） 可於本發明的研磨層4的被研磨物8側的表面設置槽加工。槽並無特別限定，可為與研磨層4的周圍連通的漿料排出槽、以及不與研磨層4的周圍連通的漿料保持槽中的任一者，另外，可具有漿料排出槽及漿料保持槽兩者。作為漿料排出槽，可列舉格子狀槽、放射狀槽等，作為漿料保持槽，可列舉同心圓狀槽、穿孔（perforation）（貫通孔）等，亦可將該些組合。 (grooving) Grooving may be provided on the surface of the polishing layer 4 of the present invention on the object-to-be-polished 8 side. The groove is not particularly limited, and may be any one of a slurry discharge groove communicating with the periphery of the polishing layer 4 and a slurry holding groove not communicating with the periphery of the polishing layer 4. In addition, a slurry discharge groove and a slurry discharge groove may be provided. Slurry holding tanks for both. Examples of the slurry discharge grooves include grid-shaped grooves and radial grooves, and examples of the slurry holding grooves include concentric circular grooves, perforation (through holes), and the like, and these may be combined.

＜緩衝層＞ （結構） 本發明的研磨墊3具有緩衝層6。緩衝層6理想的是使研磨層4向被研磨物8的抵接更均勻。作為緩衝層6的材料，可包含含浸有樹脂的含浸不織布、合成樹脂或橡膠等具有可撓性的材料、具有氣泡結構的發泡體等中的任一種。例如可列舉：聚胺基甲酸酯、聚乙烯、聚丁二烯、矽酮等樹脂或天然橡膠、腈橡膠、聚胺基甲酸酯橡膠等橡膠等。就密度及壓縮彈性係數的調整的觀點而言，較佳為含浸不織布，含浸於不織布中的樹脂材料較佳為使用聚胺基甲酸酯。 ＜Buffer layer＞ (structure) The polishing pad 3 of the present invention has a cushion layer 6 . The buffer layer 6 is ideal for making the contact of the polishing layer 4 to the object 8 to be polished more uniform. As the material of the buffer layer 6, any of resin-impregnated non-woven fabric, flexible material such as synthetic resin or rubber, foam having a cell structure, and the like may be contained. Examples thereof include resins such as polyurethane, polyethylene, polybutadiene, and silicone, and rubbers such as natural rubber, nitrile rubber, and polyurethane rubber. From the viewpoint of adjustment of density and compressive modulus, impregnated nonwoven fabric is preferred, and polyurethane is preferably used as the resin material impregnated into the nonwoven fabric.

另外，緩衝層6亦較佳地使用具有海綿狀的微細氣泡的聚胺基甲酸酯樹脂製者。In addition, the buffer layer 6 is also preferably made of polyurethane resin having spongy fine air cells.

本發明的研磨墊3中的緩衝層6的壓縮彈性係數、密度、氣泡並無特別限定，可使用具有公知的特性值的緩衝層6。The compressive modulus, density, and bubbles of the cushion layer 6 in the polishing pad 3 of the present invention are not particularly limited, and a cushion layer 6 having known property values can be used.

＜接著層＞ 接著層7是用於使緩衝層6與研磨層4接著的層，通常包含雙面膠帶或接著劑。雙面膠帶或接著劑可使用本技術領域中公知者（例如接著片）。 研磨層4及緩衝層6藉由接著層7貼合。接著層7例如可由選自丙烯酸系、環氧系、胺基甲酸酯系中的至少一種黏著劑形成。例如，可使用丙烯酸系黏著劑，厚度可設定為0.1 mm。 ＜Bonding layer＞ The adhesive layer 7 is a layer for bonding the buffer layer 6 and the polishing layer 4, and usually includes a double-sided tape or an adhesive. As the double-sided tape or adhesive, those known in the art (for example, an adhesive sheet) can be used. The polishing layer 4 and the buffer layer 6 are bonded by the adhesive layer 7 . The adhesive layer 7 can be formed of at least one adhesive selected from acrylic, epoxy, and urethane, for example. For example, an acrylic adhesive can be used and the thickness can be set to 0.1 mm.

本發明的研磨墊3的階差消除性能或瑕疵性能優異，而且耐磨耗性優異。 此處，所謂階差消除性能，是指隨著研磨而減少具有階差（凹凸）的圖案晶圓的階差的性能。將測定階差消除性能的實驗的示意圖示於圖6的（a）～圖6的（c）中。示出於被研磨物中有3500埃（angstrom）的階差的情況、使用階差消除性能高的研磨墊（虛線）及階差消除性能相對低的研磨墊（實線）的情況下的階差的消除狀態。於圖6的（a）的時間點，雖然並無差異，但是隨著研磨的進行，研磨量為2000埃時，具有良好的階差消除性能的研磨墊（虛線）與階差消除性能相對低的研磨墊（實線）相比，顯示出階差少（（b）），階差消除性能高的研磨墊相對早地消除階差（（c））。可謂虛線所示的研磨墊與實線的研磨墊相比階差消除性能相對高。 The polishing pad 3 of the present invention is excellent in step elimination performance and flaw performance, and also excellent in wear resistance. Here, the level difference elimination performance refers to the performance of reducing the level difference of a pattern wafer having a level difference (concave-convex) along with polishing. Schematic diagrams of experiments for measuring the level difference canceling performance are shown in (a) to (c) of FIG. 6 . The steps are shown in the case where there is a step difference of 3500 angstrom in the object to be polished, and when a polishing pad with high step removal performance (dotted line) and a polishing pad with relatively low step removal performance (solid line) are used. Poor elimination status. At the time point of (a) in Figure 6, although there is no difference, as the grinding progresses, when the grinding amount is 2000 angstroms, the polishing pad (dotted line) with good step elimination performance is relatively low in step elimination performance. Compared with the polishing pad (solid line), it shows less level difference ((b)), and the polishing pad with high level difference elimination performance eliminates the level difference relatively early ((c)). It can be said that the polishing pad shown by the dotted line has relatively higher level difference elimination performance than the polishing pad shown by the solid line.

另外，所謂「瑕疵」，是指包含表示附著於被研磨物的表面的細小粒子殘留而成的物質的「顆粒（Particle）」、表示附著於被研磨物的表面的研磨層的屑的「墊屑（Pad Debris）」、表示被研磨物的表面受到的損傷的「刮痕（Scratch）」等在內的缺陷的總稱，所謂瑕疵性能，是指減少該「瑕疵」的性能。In addition, the so-called "flaw" refers to "particles (Particles)" which represent the remaining fine particles attached to the surface of the object to be polished, and "pads" which represent the debris of the polishing layer attached to the surface of the object to be polished. "Pad Debris" is a general term for defects such as "scratches" that indicate damage to the surface of the object to be polished. The "scratch performance" refers to the performance of reducing the "scratch".

而且，所謂耐磨耗性，是指對於磨耗的耐性。In addition, the term "abrasion resistance" refers to resistance to abrasion.

＜＜研磨墊的製造方法＞＞ 對本發明的研磨墊3的製造方法進行說明。 ＜＜Manufacturing method of polishing pad＞＞ The method of manufacturing the polishing pad 3 of the present invention will be described.

＜研磨層的材料＞ 作為研磨層的材料，於本發明中，主成分為聚胺基甲酸酯樹脂。作為具體的主成分的材料，例如可列舉使異氰酸酯末端預聚物與硬化劑進行反應而獲得的聚胺基甲酸酯樹脂發泡體材料。 ＜Material of grinding layer＞ As a material of the polishing layer, in the present invention, the main component is polyurethane resin. As a specific material of the main component, for example, a polyurethane resin foam material obtained by reacting an isocyanate-terminated prepolymer and a curing agent is mentioned.

作為使用了異氰酸酯末端預聚物與硬化劑的研磨層4的製造方法，例如可列舉如下製造方法，所述製造方法包括：製備步驟，製備異氰酸酯末端預聚物；材料準備步驟，準備異氰酸酯末端預聚物、硬化劑、任意選擇的添加劑、及任意選擇的中空微小球體；混合步驟，將異氰酸酯末端預聚物、硬化劑、任意選擇的添加劑、及任意選擇的中空微小球體混合而獲得成形體成形用混合液；以及硬化步驟，由所述成形體成形用混合液成形研磨層。As a method of manufacturing the abrasive layer 4 using an isocyanate-terminated prepolymer and a hardener, for example, the following manufacturing method can be cited, and the manufacturing method includes: a preparation step of preparing an isocyanate-terminated prepolymer; a material preparation step of preparing an isocyanate-terminated prepolymer; Polymer, hardener, optional additive, and optional hollow microspheres; mixing step, mixing isocyanate-terminated prepolymer, hardener, optional additives, and optional hollow microspheres to obtain a molded body using a mixed solution; and a hardening step of forming an abrasive layer from the mixed solution for forming a formed body.

以下，分為製備步驟、材料準備步驟、混合步驟、成形步驟分別進行說明。Hereinafter, the preparation step, the material preparation step, the mixing step, and the molding step will be described separately.

＜製備步驟＞ 本發明中所使用的異氰酸酯末端預聚物可藉由使聚異氰酸酯化合物與聚丙二醇或聚酯二醇等高分子量多元醇進行反應而獲得，且於分子末端包含異氰酸酯基。異氰酸酯末端預聚物若有市售品則可使用市售品，通常使用使聚異氰酸酯化合物與多元醇化合物部分性地進行反應而成者作為預聚物。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，可利用對加溫至40℃的多元醇化合物，在氮氣環境下一邊攪拌一邊添加加溫至50℃的聚異氰酸酯化合物，30分鐘後升溫至80℃進而在80℃下反應60分鐘等方法來製造。 ＜Preparation steps＞ The isocyanate-terminated prepolymer used in the present invention can be obtained by reacting a polyisocyanate compound with a high molecular weight polyol such as polypropylene glycol or polyester diol, and contains an isocyanate group at a molecular terminal. As the isocyanate-terminated prepolymer, commercially available products can be used, and those obtained by partially reacting a polyisocyanate compound and a polyol compound are usually used as a prepolymer. The reaction is not particularly limited, as long as the addition polymerization reaction is performed using a known method and conditions in the production of polyurethane resins. For example, a method such as adding a polyisocyanate compound heated to 50°C to a polyol compound heated to 40°C under a nitrogen atmosphere while stirring, raising the temperature to 80°C after 30 minutes, and reacting at 80°C for 60 minutes can be used. to manufacture.

異氰酸酯末端預聚物的NCO當量並無特別限定，較佳為500～600。其原因在於：若小於500，則瑕疵性能有時惡化，若超過600，則有時無法獲得所期望的研磨速率，階差消除性能惡化。The NCO equivalent of the isocyanate-terminated prepolymer is not particularly limited, but is preferably 500-600. The reason for this is that if it is less than 500, the flaw performance may deteriorate, and if it exceeds 600, the desired polishing rate may not be obtained and the level difference elimination performance may deteriorate.

以下，對各成分進行說明。Hereinafter, each component is demonstrated.

（聚異氰酸酯化合物） 異氰酸酯末端預聚物使用聚異氰酸酯化合物作為原料。 (polyisocyanate compound) The isocyanate-terminated prepolymer uses a polyisocyanate compound as a raw material.

作為聚異氰酸酯化合物，可使用市售品，並無特別限定。 本說明書中，所謂聚異氰酸酯化合物，是指於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，只要於分子內具有兩個以上的異氰酸酯基則並無特別限制。例如作為於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-Tolylene Diisocyanate，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（Diphenylmethane-4,4'-Diisocyanate，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'-聯苯基二異氰酸酯、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、伸丙基-1,2-二異氰酸酯、伸丁基-1,2-二異氰酸酯、伸環己基-1,2-二異氰酸酯、伸環己基-1,4-二異氰酸酯、對苯二異硫氰酸酯、二甲苯-1,4-二異硫氰酸酯、次乙基二異硫氰酸酯等。該些聚異氰酸酯化合物可單獨使用，亦可組合使用多種聚異氰酸酯化合物。 As a polyisocyanate compound, a commercial item can be used, and it does not specifically limit. In this specification, a polyisocyanate compound means a compound which has two or more isocyanate groups in a molecule|numerator. The polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule. For example, examples of diisocyanate compounds having two isocyanate groups in the molecule include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-toluene diisocyanate (2,6-Tolylene Diisocyanate, 2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI), naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate (Diphenylmethane-4,4'-Diisocyanate, MDI), 4 ,4'-methylene-bis(cyclohexyl isocyanate) (hydrogenated MDI), 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenyl Methylmethane-4,4'-diisocyanate, xylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene- 1,2-diisocyanate, butyl-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, p-phenylene diisothiocyanate, Toluene-1,4-diisothiocyanate, ethylene diisothiocyanate, etc. These polyisocyanate compounds may be used alone, or a plurality of polyisocyanate compounds may be used in combination.

作為聚異氰酸酯化合物，較佳為包含2,4-TDI及/或2,6-TDI。As a polyisocyanate compound, it is preferable to contain 2,4-TDI and/or 2,6-TDI.

（作為異氰酸酯末端預聚物的原料的高分子量多元醇） 本說明書中，所謂「多元醇」，是指於分子內具有兩個或其以上的羥基（OH）的化合物。另外，所謂「高分子量」，是指分子量為500以上。 於本發明中，作為異氰酸酯末端預聚物的原料的高分子量多元醇例如可列舉：乙二醇、二乙二醇（Diethylene Glycol，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；聚酯二醇。 其中，就可調整硬鏈段間的距離的觀點、以及容易調整結晶相與非晶相的比例的觀點而言，較佳為組合使用聚丙二醇與聚酯二醇。以下，對聚丙二醇與聚酯進行說明。 (High-molecular-weight polyols used as raw materials for isocyanate-terminated prepolymers) In this specification, a "polyol" refers to a compound having two or more hydroxyl groups (OH) in the molecule. In addition, "high molecular weight" means that the molecular weight is 500 or more. In the present invention, examples of high molecular weight polyols used as raw materials for isocyanate-terminated prepolymers include diol compounds such as ethylene glycol, diethylene glycol (Diethylene Glycol, DEG), butanediol, and triol compounds; Polyether polyol compounds such as poly(oxytetramethylene) glycol (or polytetramethylene ether glycol) (PTMG); polyester diol. Among them, it is preferable to use polypropylene glycol and polyester diol in combination from the viewpoint of being able to adjust the distance between the hard segments and the ratio of the crystal phase and the amorphous phase being easily adjusted. Hereinafter, polypropylene glycol and polyester will be described.

本發明中可使用的聚丙二醇並無特別限定，例如可列舉具有500～2000、更佳為650～1000的數量平均分子量（Mn）的聚丙二醇。 再者，數量平均分子量可藉由凝膠滲透層析法（Gel Permeation Chromatography：GPC）進行測定。再者，於根據聚胺基甲酸酯樹脂測定多元醇化合物的數量平均分子量的情況下，亦可藉由胺分解等常規方法分解各成分後，藉由GPC進行推測。 The polypropylene glycol which can be used in this invention is not specifically limited, For example, the polypropylene glycol which has a number average molecular weight (Mn) of 500-2000, More preferably, it is 650-1000 is mentioned. Furthermore, the number average molecular weight can be measured by gel permeation chromatography (Gel Permeation Chromatography: GPC). In addition, when measuring the number average molecular weight of a polyol compound from a polyurethane resin, after decomposing each component by conventional methods, such as amine decomposition, it can also estimate by GPC.

於本發明中，作為異氰酸酯末端預聚物的原料的高分子量多元醇可使用聚酯二醇。本說明書中，聚酯二醇具有兩個以上的酯鍵與兩個羥基（OH）。 聚酯二醇例如可藉由使二羧酸化合物與二醇化合物進行反應而獲得。 作為二羧酸化合物，可列舉：琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸等脂肪族二羧酸；馬來酸酐、馬來酸、富馬酸等含有不飽和鍵的二羧酸；1,3-環戊烷二羧酸、1,4-環己烷二羧酸等脂環族多元羧酸；鄰苯二甲酸、對苯二甲酸、間苯二甲酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、萘二甲酸、聯苯基二羧酸、聯苯甲酸及該些的酐等芳香族二羧酸等，可單獨使用，亦可組合使用。 In the present invention, polyester diol can be used as the high-molecular-weight polyol as a raw material of the isocyanate-terminated prepolymer. In this specification, polyester diol has two or more ester bonds and two hydroxyl groups (OH). Polyester diol can be obtained by making a dicarboxylic acid compound and a diol compound react, for example. Examples of dicarboxylic acid compounds include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; Anhydride, maleic acid, fumaric acid and other dicarboxylic acids containing unsaturated bonds; 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and other alicyclic polycarboxylic acids; o-phthalic acid Dicarboxylic acid, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid Aromatic dicarboxylic acids such as , biphenylcarboxylic acid, and their anhydrides may be used alone or in combination.

作為聚酯二醇的合成中所使用的二醇化合物，可列舉：乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇等，可單獨使用亦可組合使用。Examples of diol compounds used in the synthesis of polyester diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1 ,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 - Hexylene glycol and the like may be used alone or in combination.

所述中，較佳為己二酸與1,4-丁二醇的聚酯二醇、以及己二酸與二乙二醇的聚酯二醇。Among the above, polyester diol of adipic acid and 1,4-butanediol, and polyester diol of adipic acid and diethylene glycol are preferred.

就作為軟鏈段而顯示出研磨墊所需的橡膠彈性的觀點而言，聚酯二醇的數量平均分子量較佳為600～2500。The number average molecular weight of the polyester diol is preferably from 600 to 2,500 from the viewpoint of exhibiting rubber elasticity required for a polishing pad as a soft segment.

相對於高分子量多元醇整體，聚丙二醇較佳為小於60重量%。於60重量%以上的情況下，耐磨耗性有時會變差。較佳為相對於高分子量多元醇整體，聚丙二醇為30重量%～50重量%。 另外，相對於高分子量多元醇整體，聚酯二醇較佳為70重量%以下。若超過70重量%，則階差消除性能有時會變差。較佳為相對於高分子量多元醇整體，聚酯二醇為50重量%～70重量%。 相對於高分子量多元醇整體，聚丙二醇與聚酯二醇的合計量較佳為80重量%以上。原因在於：若為80重量%以上，則顯著地顯現出效果。 The polypropylene glycol is preferably less than 60% by weight relative to the whole high molecular weight polyol. When it is 60 weight% or more, abrasion resistance may worsen. It is preferable that polypropylene glycol is 30 weight% - 50 weight% with respect to the whole high molecular weight polyol. Moreover, it is preferable that polyester diol is 70 weight% or less with respect to the whole high molecular weight polyol. If it exceeds 70% by weight, the level difference canceling performance may deteriorate. It is preferable that polyester diol is 50 weight% - 70 weight% with respect to the whole high molecular weight polyol. The total amount of polypropylene glycol and polyester diol is preferably 80% by weight or more based on the entire high-molecular-weight polyol. The reason is that the effect is remarkably exhibited if it is 80% by weight or more.

於本發明中，作為高分子量多元醇，亦可使用聚氧基四亞甲基二醇等，相對於高分子量多元醇整體，較佳為10重量%以下，更佳為5重量%以下，進而佳為3重量%以下。若超過10重量%而包含，則有時階差消除性能或瑕疵性能變得不充分。In the present invention, polyoxytetramethylene glycol and the like can also be used as the high molecular weight polyol, and it is preferably 10% by weight or less, more preferably 5% by weight or less, with respect to the whole high molecular weight polyol. Preferably, it is 3% by weight or less. When it is contained in excess of 10% by weight, the level difference elimination performance or flaw performance may become insufficient.

＜材料準備步驟＞ 為了製造本發明的研磨層4，準備異氰酸酯末端預聚物、硬化劑、任意選擇的添加劑、及任意選擇的中空微小球體。關於異氰酸酯末端預聚物，已經進行了說明，因此，此處對硬化劑、添加劑、及中空微小球體進行說明。 ＜Material preparation procedure＞ In order to manufacture the polishing layer 4 of the present invention, an isocyanate-terminated prepolymer, a curing agent, optionally selected additives, and optionally selected hollow microspheres are prepared. The isocyanate-terminated prepolymer has already been described, so the curing agent, additives, and hollow microspheres will be described here.

（硬化劑） 本發明的研磨層4的製造方法中，於混合步驟中使硬化劑（亦稱為鏈伸長劑）與異氰酸酯末端預聚物等混合。藉由加入硬化劑，於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，可進行硬化。 作為硬化劑，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（MOCA）、4-甲基-2,6-雙(甲硫基)-1,3-苯二胺、2-甲基-4,6-雙(甲硫基)-1,3-苯二胺、2,2-雙(3-胺基-4-羥基苯基)丙烷、2,2-雙[3-(異丙基胺基)-4-羥基苯基]丙烷、2,2-雙[3-(1-甲基丙基胺基)-4-羥基苯基]丙烷、2,2-雙[3-(1-甲基戊基胺基)-4-羥基苯基]丙烷、2,2-雙(3,5-二胺基-4-羥基苯基)丙烷、2,6-二胺基-4-甲基苯酚、三甲基伸乙基雙-4-胺基苯甲酸酯、以及聚四亞甲基氧化物-二-對胺基苯甲酸酯等多元胺化合物；乙二醇、丙二醇、二乙二醇、三亞甲基二醇、四乙二醇、三乙二醇、二丙二醇、1,4-丁二醇、1,3-丁二醇、2,3-丁二醇、1,2-丁二醇、3-甲基-1,2-丁二醇、1,2-戊二醇、1,4-戊二醇、2,4-戊二醇、2,3-二甲基三亞甲基二醇、四亞甲基二醇、3-甲基-4,3-戊二醇、3-甲基-4,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,6-己二醇、1,5-己二醇、1,4-己二醇、2,5-己二醇、1,4-環己烷二甲醇、新戊二醇、甘油、三羥甲基丙烷、三羥甲基乙烷、三羥甲基甲烷、聚(氧基四亞甲基)二醇、聚乙二醇、及聚丙二醇等多元醇化合物。另外，多元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。作為多元胺化合物，較佳為二胺化合物，進而佳為使用例如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）。 (hardener) In the method for producing the polishing layer 4 of the present invention, a hardener (also referred to as a chain extender) is mixed with an isocyanate-terminated prepolymer and the like in the mixing step. By adding a curing agent, the end of the main chain of the polyisocyanate compound containing a urethane bond is bonded to the curing agent to form a polymer chain in the subsequent molded body forming step, thereby enabling curing. Examples of curing agents include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, 3,3'-dichloro -4,4'-diaminodiphenylmethane (MOCA), 4-methyl-2,6-bis(methylthio)-1,3-phenylenediamine, 2-methyl-4,6- Bis(methylthio)-1,3-phenylenediamine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[3-(isopropylamino)- 4-Hydroxyphenyl]propane, 2,2-bis[3-(1-methylpropylamino)-4-hydroxyphenyl]propane, 2,2-bis[3-(1-methylpentyl) Amino)-4-hydroxyphenyl]propane, 2,2-bis(3,5-diamino-4-hydroxyphenyl)propane, 2,6-diamino-4-methylphenol, trimethyl Polyamine compounds such as ethylidene bis-4-aminobenzoate and polytetramethylene oxide-di-p-aminobenzoate; Methyl glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, Tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol , 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, Polyol compounds such as trimethylolpropane, trimethylolethane, trimethylolmethane, poly(oxytetramethylene) glycol, polyethylene glycol, and polypropylene glycol. In addition, the polyvalent amine compound may have a hydroxyl group, and examples of such amine compounds include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di - 2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and the like. As the polyamine compound, diamine compounds are preferable, and for example, 3,3'-dichloro-4,4'-diaminodiphenylmethane (methylene bis-o-chloroaniline) (hereinafter, Abbreviated as MOCA).

（添加劑） 作為研磨層4的材料，可根據需要添加氧化劑等添加劑。於本發明中，若不是阻礙本發明的效果的物質，則並無特別限定。 (additive) As the material of the polishing layer 4, additives such as an oxidizing agent may be added as necessary. In the present invention, it is not particularly limited unless it inhibits the effect of the present invention.

（中空微小球體） 研磨層4根據需要包含具有外殼、且內部為中空狀的中空微小球體4A。如上所述，作為中空微小球體4A的材料，可使用市售品。或者，亦可使用藉由利用常規方法進行合成而獲得者。作為中空微小球體4A的外殼的材質，並無特別限制，例如可列舉：聚乙烯基醇、聚乙烯基吡咯啶酮、聚(甲基)丙烯酸、聚丙烯醯胺、聚乙二醇、聚羥基醚丙烯酸酯、馬來酸共聚物、聚環氧乙烷、聚胺基甲酸酯、聚(甲基)丙烯腈、聚偏二氯乙烯、聚氯乙烯及有機矽酮系樹脂、以及將構成該些樹脂的單量體組合兩種以上而成的共聚物。另外，作為市售品的中空微小球體，不限定於以下，例如可列舉埃克斯帕塞爾系列（Expancel Series）（阿克蘇諾貝爾（Akzo Nobel）公司製造的商品名）、松本微球（Matsumoto Microsphere）（松本油脂（股）公司製造的商品名）等。 (hollow tiny spheres) The abrasive layer 4 includes hollow microspheres 4A having an outer shell and having a hollow interior as needed. As described above, commercially available materials can be used as the material of the hollow microspheres 4A. Alternatively, those obtained by synthesis by conventional methods can also be used. The material of the shell of the hollow microsphere 4A is not particularly limited, for example, polyvinyl alcohol, polyvinylpyrrolidone, poly(meth)acrylic acid, polyacrylamide, polyethylene glycol, polyhydroxy Ether acrylate, maleic acid copolymer, polyethylene oxide, polyurethane, poly(meth)acrylonitrile, polyvinylidene chloride, polyvinyl chloride and organic silicone resin, and will constitute A copolymer in which two or more monomers of these resins are combined. In addition, the hollow microspheres that are commercially available are not limited to the following, for example, Expancel Series (trade name manufactured by Akzo Nobel), Matsumoto Microspheres (Matsumoto Microsphere) (trade name manufactured by Matsumoto Yushi Co., Ltd.), etc.

中空微小球體4A的材料以相對於異氰酸酯末端預聚物100質量份成為較佳為0.1質量份～10質量份、更佳為1質量份～5質量份、進而更佳為1質量份～3質量份的方式添加。The material of the hollow microsphere 4A is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass relative to 100 parts by mass of the isocyanate-terminated prepolymer. added as copies.

另外，除了所述成分以外，亦可於不損害本發明的效果的範圍內，將先前所使用的發泡劑與中空微小球體4A併用，亦可於下述混合步驟中吹入對於所述各成分而言為非反應性的氣體。作為該發泡劑，除了水以外，亦可列舉以碳數5或6的烴為主成分的發泡劑。作為該烴，例如可列舉正戊烷、正己烷等鏈狀烴、或環戊烷、環己烷等脂環式烴。In addition, in addition to the above-mentioned components, the previously used blowing agent and the hollow microspheres 4A may also be used in combination within the range not impairing the effect of the present invention, and it is also possible to blow in the following mixing step. Compositionally non-reactive gas. Examples of the foaming agent include, in addition to water, those mainly composed of hydrocarbons having 5 or 6 carbon atoms. Examples of the hydrocarbons include chain hydrocarbons such as n-pentane and n-hexane, and alicyclic hydrocarbons such as cyclopentane and cyclohexane.

關於製造預聚物的方法，例如可將聚異氰酸酯化合物、聚丙二醇、以及聚酯二醇混合並進行反應，亦可藉由將聚異氰酸酯化合物與聚丙二醇的混合物1、和聚異氰酸酯化合物與聚酯二醇的混合物2混合而進行反應。Regarding the method for producing the prepolymer, for example, a polyisocyanate compound, polypropylene glycol, and polyester diol may be mixed and reacted, or a mixture 1 of a polyisocyanate compound and polypropylene glycol, and a polyisocyanate compound and polyester The mixture of diols 2 is mixed and reacted.

＜混合步驟＞ 於混合步驟中，將所述準備步驟中所獲得的異氰酸酯末端預聚物、硬化劑、任意選擇的添加劑、任意選擇的中空微小球體供給至混合機內並進行攪拌、混合。混合步驟是在加溫至可確保所述各成分的流動性的溫度的狀態下進行，但若過度加熱，則中空微小球體會膨脹，會變得不具有規定的開口分佈，因此需要注意。 ＜Mixing procedure＞ In the mixing step, the isocyanate-terminated prepolymer obtained in the preparation step, the curing agent, optional additives, and arbitrarily selected hollow microspheres are fed into a mixer and stirred and mixed. The mixing step is carried out under heating to a temperature at which the fluidity of the above-mentioned components can be ensured. However, if the heating is excessive, the hollow microspheres will expand and the predetermined opening distribution will not be obtained. Therefore, caution is required.

＜成形步驟＞ 成形體成形步驟中，將所述混合步驟中製備的成形體成形用混合液流入到預熱至30℃～100℃的模框內使其一次硬化，之後在100℃～150℃左右進行10分鐘～5小時左右的加熱，使其二次硬化，藉此將硬化後的聚胺基甲酸酯樹脂（聚胺基甲酸酯樹脂成形體）成形。此時，藉由異氰酸酯末端預聚物、硬化劑進行反應並形成聚胺基甲酸酯樹脂發泡體，從而該混合液硬化。 異氰酸酯末端預聚物若黏度過高，則流動性變差，混合時難以大致均勻地混合。若溫度上升、黏度下降，則適用期變短，反而產生混合不均，所獲得的發泡體中所含的中空微小球體的大小產生偏差。尤其是，若反應溫度過高，則於使用未膨脹型的中空微小球體的情況下，會過度膨脹，無法獲得所期望的開孔。相反，若黏度過低，則氣泡會在混合液中移動，難以獲得中空微小球體大致均等地分散的發泡體。因此，異氰酸酯末端預聚物較佳為將溫度50℃～80℃下的黏度設定為500 mPa·s～4000 mPa·s的範圍。該情況例如可藉由改變異氰酸酯末端預聚物的分子量（聚合度）來設定黏度。異氰酸酯末端預聚物被加熱至50℃～80℃左右而成為能夠流動的狀態。 ＜Forming step＞ In the molded body forming step, the mixed solution for molding the molded body prepared in the mixing step is poured into a mold frame preheated to 30°C to 100°C to make it harden once, and then it is carried out at about 100°C to 150°C for 10 minutes. Heat for about 5 hours to make it secondary harden, and thereby mold the cured polyurethane resin (polyurethane resin molded article). At this time, the isocyanate-terminated prepolymer and the curing agent react to form a polyurethane resin foam, and the mixed solution is cured. If the viscosity of the isocyanate-terminated prepolymer is too high, fluidity will deteriorate, and it will be difficult to mix it almost uniformly during mixing. When the temperature rises and the viscosity falls, the pot life becomes short, uneven mixing occurs instead, and the size of the hollow microspheres contained in the obtained foam varies. In particular, if the reaction temperature is too high, when unexpanded hollow microspheres are used, they will expand excessively, and desired openings will not be obtained. Conversely, if the viscosity is too low, air bubbles will move in the liquid mixture, making it difficult to obtain a foam in which hollow microspheres are dispersed substantially uniformly. Therefore, the isocyanate-terminated prepolymer preferably has a viscosity in a range of 500 mPa·s to 4000 mPa·s at a temperature of 50°C to 80°C. In this case, for example, the viscosity can be set by changing the molecular weight (polymerization degree) of the isocyanate-terminated prepolymer. The isocyanate-terminated prepolymer is heated to about 50° C. to 80° C. to be in a flowable state.

於成形步驟中，根據需要，使澆注的混合液在模框內反應，形成發泡體。此時，藉由異氰酸酯末端預聚物與硬化劑的反應，異氰酸酯末端預聚物交聯硬化。In the forming step, if necessary, the poured mixed solution is reacted in the frame to form a foam. At this time, the isocyanate-terminated prepolymer is cross-linked and cured by the reaction between the isocyanate-terminated prepolymer and the curing agent.

於獲得成形體後，切成片狀，形成多片研磨層4。切片可使用一般的切片機。切片時保持研磨層4的下層部分，自上層部開始依次切成規定厚度。進行切片的厚度例如設定為1.3 mm～2.5 mm的範圍內。於厚度為50 mm的利用模框成型的發泡體中，例如發泡體的上層部及下層部的約10 mm的部分由於傷痕等關係而不使用，由中央部的約30 mm的部分形成10片～25片研磨層4。於硬化成型步驟中獲得在內部大致均等地形成有中空微小球體4A的發泡體。After the molded body is obtained, it is cut into sheets to form multiple abrasive layers 4 . A general slicer can be used for slicing. When slicing, keep the lower part of the abrasive layer 4, and cut into a predetermined thickness sequentially from the upper part. The thickness at which to slice is set within a range of, for example, 1.3 mm to 2.5 mm. In a foam molded with a thickness of 50 mm, for example, about 10 mm of the upper and lower layers of the foam are not used due to scratches, etc., and formed by about 30 mm of the central part 10 to 25 abrasive layers 4 . In the hardening molding step, a foam in which the hollow microspheres 4A are substantially uniformly formed inside is obtained.

亦可根據需要對所獲得的研磨層4的研磨面實施槽加工。於本發明中，槽加工的方法及其形狀並無特別限定。Grooving may be performed on the polished surface of the obtained polishing layer 4 as needed. In the present invention, the groove processing method and its shape are not particularly limited.

關於如此獲得的研磨層4，其後於研磨層4的與研磨面為相反側的面貼附雙面膠帶。雙面膠帶並無特別限制，可自本技術領域中公知的雙面膠帶中任意選擇來使用。With regard to the polishing layer 4 obtained in this way, a double-sided tape is then attached to the surface of the polishing layer 4 that is on the opposite side to the polishing surface. The double-sided tape is not particularly limited, and any double-sided tape known in the art can be used.

＜緩衝層6的製造方法＞ 緩衝層6較佳為包含含浸樹脂而成的含浸不織布。作為含浸於不織布中的樹脂，較佳為可列舉：聚胺基甲酸酯及聚胺基甲酸酯聚脲等聚胺基甲酸酯系、聚丙烯酸酯及聚丙烯腈等丙烯酸系、聚氯乙烯、聚乙酸乙烯基酯及聚偏二氟乙烯等乙烯基系、聚碸及聚醚碸等聚碸系、乙醯化纖維素及丁醯化纖維素等醯化纖維素系、聚醯胺系以及聚苯乙烯系等。關於不織布的密度，於樹脂含浸前的狀態（料片的狀態）下，較佳為0.3 g/cm ³以下，更佳為0.1 g/cm ³～0.2 g/cm ³。另外，樹脂含浸後的不織布的密度較佳為0.7 g/cm ³以下，更佳為0.25 g/cm ³～0.5 g/cm ³。藉由樹脂含浸前及樹脂含浸後的不織布的密度為所述上限以下，加工精度提高。另外，藉由樹脂含浸前及樹脂含浸後的不織布的密度為所述下限以上，可減少研磨漿料浸透至基材層的情況。樹脂對於不織布的附著率由相對於不織布的重量的所附著的樹脂的重量表示，較佳為50重量%以上，更佳為75重量%～200重量%。藉由樹脂對於不織布的附著率為所述上限以下，可具有所期望的緩衝性。 <The manufacturing method of the buffer layer 6> It is preferable that the buffer layer 6 is the impregnated nonwoven fabric containing impregnated resin. As the resin to be impregnated into the nonwoven fabric, preferably, polyurethanes such as polyurethane and polyurethane polyurea, acrylics such as polyacrylate and polyacrylonitrile, poly Vinyl systems such as vinyl chloride, polyvinyl acetate, and polyvinylidene fluoride; Polyethylene systems such as polyethers and polyether fibers; Acetyl cellulose systems such as acetylated cellulose and butylated cellulose; Polyamides Amine-based and polystyrene-based, etc. The density of the nonwoven fabric is preferably 0.3 g/cm ³ or less, more preferably 0.1 g/cm ³ to 0.2 g/cm ³ in the state before resin impregnation (state of the web). In addition, the density of the resin-impregnated nonwoven fabric is preferably at most 0.7 g/cm ³ , more preferably 0.25 g/cm ³ to 0.5 g/cm ³ . When the density of the nonwoven fabric before resin impregnation and after resin impregnation is below the said upper limit, processing precision improves. Moreover, when the density of the nonwoven fabric before resin impregnation and after resin impregnation is more than the said minimum, it can reduce that a polishing slurry penetrates into a base material layer. The adhesion rate of the resin to the nonwoven fabric is represented by the weight of the attached resin relative to the weight of the nonwoven fabric, and is preferably 50% by weight or more, more preferably 75% by weight to 200% by weight. When the adhesion rate of the resin to the nonwoven fabric is not more than the above-mentioned upper limit, desired cushioning properties can be obtained.

＜接合步驟＞ 於接合步驟中，利用接著層7將所形成的研磨層4及緩衝層6貼合（接合）。接著層7例如使用丙烯酸系黏著劑，且以厚度成為0.1 mm的方式形成接著層7。即，於研磨層4的與研磨面為相反側的面以大致均勻的厚度塗佈丙烯酸系黏著劑。將研磨層4的與研磨面為相反側的面和緩衝層6的表面經由所塗佈的黏著劑壓接，從而利用接著層7將研磨層4及緩衝層6貼合。然後，於裁斷成圓形等所期望的形狀後，進行對無污垢或異物等的附著加以確認等檢查，從而完成研磨墊3。 [實施例] ＜Joining procedure＞ In the bonding step, the formed polishing layer 4 and buffer layer 6 are bonded (bonded) by the adhesive layer 7 . For example, an acrylic adhesive is used for the adhesive layer 7 , and the adhesive layer 7 is formed so as to have a thickness of 0.1 mm. That is, the acrylic adhesive is applied to the surface of the polishing layer 4 opposite to the polishing surface with a substantially uniform thickness. The surface of the polishing layer 4 opposite to the polishing surface and the surface of the buffer layer 6 are pressure-bonded through the applied adhesive, and the polishing layer 4 and the buffer layer 6 are bonded together by the adhesive layer 7 . Then, after cutting into a desired shape such as a circle, inspections such as checking whether there is no adhesion of dirt or foreign matter are performed to complete the polishing pad 3 . [Example]

以下，藉由實施例更詳細地說明本發明，但本發明不受該些例子的限定。Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these examples.

於各實施例及比較例中，只要無特別指定，則所謂「份」，是指「質量份」。In each of the Examples and Comparative Examples, unless otherwise specified, "parts" means "parts by mass".

另外，所謂NCO當量，是表示利用「（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一分子的官能基數×聚異氰酸酯化合物的質量（份）/聚異氰酸酯化合物的分子量）-（多元醇化合物每一分子的官能基數×多元醇化合物的質量（份）/多元醇化合物的分子量）]」求出的每一個NCO基的預聚物（Prepolymer，PP）的分子量的數值。In addition, the so-called NCO equivalent is expressed by "(mass (parts) of polyisocyanate compound + mass (parts) of polyol compound)/[(number of functional groups per molecule of polyisocyanate compound x mass (parts) of polyisocyanate compound) /Molecular weight of polyisocyanate compound)-(The number of functional groups per molecule of polyol compound×The mass of polyol compound (parts)/Molecular weight of polyol compound)]” The prepolymer of each NCO group (Prepolymer, PP) molecular weight value.

[實施方式1] （研磨層的製造） 於使2,4-甲苯二異氰酸酯（TDI）、表1中所示的高分子量多元醇進行反應而成的NCO當量為520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、且殼內內包有異丁烷氣體的已膨脹型的中空微小球體3份，獲得混合液。將所獲得的混合液裝入至第一液罐中，進行保溫。其次，獨立於第一液，另行將作為硬化劑的MOCA 23.1份裝入至第二液罐中，於第二液罐內進行保溫。將第一液罐、第二液罐各自的液體以表示硬化劑中所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，自包括兩個注入口的混合機的各注入口注入至所述混合機。將注入的兩種液體一邊混合攪拌一邊注入到預熱至80℃的成形機的模具，之後，進行合模，加熱30分鐘，進行一次硬化。將一次硬化後的成形物脫模後，利用烘箱在120℃下進行4小時二次硬化，獲得胺基甲酸酯成形物。於將所獲得的胺基甲酸酯成形物放置冷卻至25℃後，再次利用烘箱於120℃下加熱5小時後切成1.3 mm的厚度，獲得與實施例及比較例對應的研磨層。 [Embodiment 1] (Manufacture of grinding layer) To 100 parts of an isocyanate group-terminated urethane prepolymer with an NCO equivalent of 520, which was obtained by reacting 2,4-toluene diisocyanate (TDI) and a high-molecular-weight polyol shown in Table 1, add and mix The shell portion contained acrylonitrile-vinylidene chloride copolymer, and 3 parts of expanded hollow microspheres were filled with isobutane gas to obtain a mixed liquid. The obtained mixed liquid is charged into the first liquid tank and kept warm. Next, separately from the first liquid, 23.1 parts of MOCA as a hardening agent was separately put into the second liquid tank, and kept warm in the second liquid tank. The respective liquids of the first liquid tank and the second liquid tank are self-contained in such a manner that the R value representing the equivalent ratio of the amine group and the hydroxyl group present in the curing agent to the terminal isocyanate group in the prepolymer becomes 0.90. Injection Ports Each injection port of the mixer injects into the mixer. The injected two liquids were poured into the mold of the molding machine preheated to 80°C while mixing and stirring, and then the molds were closed and heated for 30 minutes to perform primary hardening. After demoulding the primary cured molded product, secondary curing was performed in an oven at 120° C. for 4 hours to obtain a urethane molded product. After cooling the obtained urethane molded product to 25° C., it was heated again in an oven at 120° C. for 5 hours, and then cut into a thickness of 1.3 mm to obtain polishing layers corresponding to Examples and Comparative Examples.

（緩衝層的製造） 將包含聚酯纖維的不織布浸漬於胺基甲酸酯樹脂溶液（迪愛生（DIC）公司製造，商品名「C1367」）中。於浸漬後，使用能夠對一對輥間加壓的軋液輥（mangle roller），將樹脂溶液擠出，使樹脂溶液大致均勻地含浸於不織布中。繼而，藉由浸漬於包含室溫的水的凝固液中，而使含浸樹脂凝固再生，獲得樹脂含浸不織布。其後，自凝固液中取出樹脂含浸不織布，進而浸漬於包含水的清洗液中，去除樹脂中的N,N-二甲基甲醯胺（N,N-Dimethyl Formamide，DMF）後，加以乾燥。於乾燥後，藉由拋光（buffing）處理去除表面的表層，製作厚度為1.3 mm的緩衝層。 (Manufacture of buffer layer) A nonwoven fabric containing polyester fibers was dipped in a urethane resin solution (manufactured by DIC, trade name "C1367"). After impregnation, the resin solution is extruded using a mangle roller capable of pressurizing between a pair of rolls, and the nonwoven fabric is impregnated substantially uniformly with the resin solution. Then, the impregnated resin was coagulated and regenerated by immersing in a coagulating solution containing water at room temperature to obtain a resin-impregnated nonwoven fabric. Thereafter, the resin-impregnated nonwoven fabric is taken out from the coagulation solution, and then immersed in a cleaning solution containing water to remove N,N-dimethylformamide (N,N-Dimethyl Formamide, DMF) in the resin, and then dried . After drying, the surface layer was removed by buffing to make a buffer layer with a thickness of 1.3 mm.

（實施例及比較例） 利用厚度為0.1 mm的雙面膠帶（於聚對苯二甲酸乙二酯（polyethylene terephthalate，PET）基材的兩面包括包含丙烯酸系樹脂的接著劑者）將由表1所示的成分形成的各研磨層及緩衝層接合，製造實施例1～實施例4及比較例1～比較例3的研磨墊。另外，使用先前公知的研磨墊IC1000（霓塔哈斯（Nitta Haas）公司製造）作為比較例4。 另外，酯A表示使己二酸與二乙二醇進行反應而獲得的數量平均分子量為1000的聚酯二醇，酯B表示使己二酸與丁二醇進行反應而獲得的數量平均分子量為1000的聚酯二醇，PPG表示數量平均分子量為1000的聚丙二醇 (Example and Comparative Example) Using a double-sided adhesive tape with a thickness of 0.1 mm (including an adhesive containing an acrylic resin on both sides of a polyethylene terephthalate (PET) base material), grind each of the components shown in Table 1 The layer and the cushion layer were bonded together, and the polishing pads of Examples 1 to 4 and Comparative Examples 1 to 3 were produced. In addition, as Comparative Example 4, a conventionally known polishing pad IC1000 (manufactured by Nitta Haas) was used. In addition, ester A represents polyester diol with a number average molecular weight of 1000 obtained by reacting adipic acid and diethylene glycol, and ester B represents a number average molecular weight obtained by reacting adipic acid with butanediol. 1000 polyester diol, PPG means polypropylene glycol with a number average molecular weight of 1000

[表1]    預聚物 硬化劑 R值 密度 （g/cm ³） D硬度 （°） 高分子量多元醇重量比 PPG調配比 NCO當量 實施例1 PPG：酯A=5：5 50 520 MOCA 0.90 0.84 46.0 實施例2 PPG：酯A=3：7 30 0.86 47.0 實施例3 PPG：酯B=5：5 50 0.82 46.5 實施例4 PPG：酯B=3：7 30 0.80 45.5 比較例1 PPG：100% 100 0.84 49.5 比較例2 PPG：酯A=7：3 70 0.86 47.0 比較例3 PPG：酯B=7：3 70 0.83 43.5 [Table 1] prepolymer hardener R value Density (g/cm ³ ) D hardness (°) High Molecular Weight Polyol Weight Ratio PPG mix ratio NCO equivalent Example 1 PPG:ester A=5:5 50 520 MOCA 0.90 0.84 46.0 Example 2 PPG:ester A=3:7 30 0.86 47.0 Example 3 PPG:ester B=5:5 50 0.82 46.5 Example 4 PPG:ester B=3:7 30 0.80 45.5 Comparative example 1 PPG: 100% 100 0.84 49.5 Comparative example 2 PPG:ester A=7:3 70 0.86 47.0 Comparative example 3 PPG:ester B=7:3 70 0.83 43.5

（密度） 研磨層的密度（g/cm ³）是依據日本工業標準（Japanese Industrial Standards）（JIS K 6505）進行測定。 (Density) The density (g/cm ³ ) of the polishing layer was measured in accordance with Japanese Industrial Standards (JIS K 6505).

（D硬度） 研磨層的D硬度是依據日本工業標準（JIS-K-6253），使用D型硬度計進行測定。此處，測定試樣是藉由以至少總厚度成為4.5 mm以上的方式根據需要將多片研磨層重疊而獲得。 (D hardness) The D hardness of the abrasive layer was measured using a D-type hardness tester in accordance with Japanese Industrial Standards (JIS-K-6253). Here, the measurement sample is obtained by laminating a plurality of polishing layers as needed so that at least the total thickness becomes 4.5 mm or more.

（磨耗試驗） 對於所獲得的研磨墊，使用小型摩擦磨耗試驗機，於下述條件下進行磨耗試驗。將縱軸取磨耗量（厚度）、橫軸取PPG調配比率的圖示於圖7中。 (wear test) The obtained polishing pad was subjected to an abrasion test under the following conditions using a small friction and abrasion tester. FIG. 7 shows a graph in which the wear amount (thickness) is taken on the vertical axis and the PPG compounding ratio is taken on the horizontal axis.

（磨耗試驗條件） 使用研磨機：小型摩擦磨耗試驗機 壓頭側：PAD（17ϕ） 壓盤側：#180砂紙 載荷：300 g 液體：水 流量：45 ml/分鐘 壓盤轉數：40 rpm 時間：10分鐘 厚度測定載荷：300 g (Abrasion test conditions) Grinding machine used: small friction and wear testing machine Indenter side: PAD (17ϕ) Platen side: #180 sandpaper Load: 300g liquid: water Flow rate: 45 ml/min Platen revolutions: 40 rpm Time: 10 minutes Thickness measurement load: 300 g

如由圖7得知般，若提高高分子量多元醇中的PPG調配比率，則磨耗量變大，耐磨耗性惡化。於PPG的調配比率小於60重量%的情況下，磨耗量的增加得到抑制。另一方面，若PPG的調配比率超過60重量%，則磨耗量急劇地增加。該傾向於酯A及酯B中的任一者中均相同。另外，於小於60重量%的情況下，與先前公知的比較例4的研磨墊（0.10 mm）為同等程度。 再者，將酯A及酯B的調配比率設為100%者的後述的階差消除性能差。 As can be seen from FIG. 7 , when the blending ratio of PPG in the high-molecular-weight polyol is increased, the amount of abrasion increases and the abrasion resistance deteriorates. When the blending ratio of PPG is less than 60% by weight, the increase in the amount of abrasion is suppressed. On the other hand, when the blending ratio of PPG exceeds 60% by weight, the amount of wear increases rapidly. This tendency is the same for both the ester A and the ester B. Moreover, when it is less than 60 weight%, it is equivalent to the polishing pad (0.10 mm) of the conventionally well-known comparative example 4. In addition, when the compounding ratio of ester A and ester B was set to 100%, the step elimination performance mentioned later was inferior.

（研磨性能評價） 使用所獲得的實施例1、比較例1及比較例4的研磨墊，於下述研磨條件下實施研磨試驗。 (Grinding Performance Evaluation) Using the obtained polishing pads of Example 1, Comparative Example 1, and Comparative Example 4, a polishing test was implemented under the following polishing conditions.

（研磨條件） 使用研磨機：F-REX300X（荏原製作所公司製造） 盤（Disk）：A188（3M公司製造） 研磨劑溫度：20℃ 研磨壓盤轉數：85 rpm 研磨頭轉數：86 rpm 研磨壓力：3.5 psi 研磨漿料（金屬膜）：CSL-9044C（使用CSL-9044C原液：純水=重量比1：9的混合液）（福吉米公司（Fujimi Corporation）製造） 研磨漿料流量：200 ml/min 研磨時間：60秒 被研磨物（金屬膜）：Cu膜基板 墊磨合（pad break）：35 N 10分鐘 調節（conditioning）：異位（Ex-situ）、35 N、4次掃描（scan） (grinding condition) Grinder used: F-REX300X (manufactured by Ebara Seisakusho) Disk (Disk): A188 (manufactured by 3M Company) Abrasive temperature: 20°C Grinding platen revolutions: 85 rpm Grinding head rotation speed: 86 rpm Grinding Pressure: 3.5 psi Polishing slurry (metal film): CSL-9044C (use CSL-9044C stock solution: pure water = mixed solution with a weight ratio of 1:9) (manufactured by Fujimi Corporation) Grinding slurry flow: 200 ml/min Grinding time: 60 seconds Object to be polished (metal film): Cu film substrate Pad break: 35 N for 10 minutes Conditioning: Ex-situ, 35 N, 4 scans

（階差消除性能試驗） 將研磨墊經由具有丙烯酸系接著劑的雙面膠帶而設置於研磨裝置的規定位置，於所述研磨條件下實施研磨加工。階差消除性能是藉由利用階差/表面粗糙度/微細形狀測定裝置（科磊（KLA Tencor）公司製造，P-16+）對100 μm/100 μm的凹陷（dishing）進行測定來評價。將評價結果示於圖8中。 對於具有7000埃的膜厚、3000埃的階差的圖案晶圓，以一次研磨量成為1000埃的方式調整研磨速率，並實施研磨，階段性地進行研磨，每次實施晶圓的階差測定。縱軸的台階高度（Step Height）表示階差。 圖8中，左上的120 μm是配線寬度為120 μm的配線，右上的100/100是相對於Cu配線寬度100 μm而言絕緣膜的寬度為100 μm的配線，左下的50/50是相對於Cu配線寬度50 μm而言絕緣膜的寬度為50 μm的配線，右下的10/10是相對於Cu配線寬度10 μm而言絕緣膜的寬度為10 μm的配線，數字越小，配線變得越微細。 (Stand difference elimination performance test) A polishing pad was installed at a predetermined position of a polishing apparatus through a double-sided tape having an acrylic adhesive, and polishing was performed under the above-mentioned polishing conditions. The level difference elimination performance was evaluated by measuring 100 μm/100 μm dishing with a level difference/surface roughness/micro shape measuring device (manufactured by KLA Tencor, P-16+). The evaluation results are shown in FIG. 8 . For a patterned wafer having a film thickness of 7000 angstroms and a step difference of 3000 angstroms, the polishing rate was adjusted so that the amount of polishing at one time became 1000 angstroms, and polishing was performed in stages, and the level difference measurement of the wafer was performed each time . The step height (Step Height) on the vertical axis represents the step difference. In Figure 8, 120 μm on the upper left is a wiring with a wiring width of 120 μm, 100/100 on the upper right is a wiring with an insulating film width of 100 μm relative to a Cu wiring width of 100 μm, and 50/50 on the lower left is a wiring with a width of 100 μm compared to Cu wiring. The Cu wiring width is 50 μm and the insulating film width is 50 μm. The 10/10 on the lower right is the wiring whose insulating film width is 10 μm relative to the Cu wiring width of 10 μm. The smaller the number, the wiring becomes The finer it is.

（瑕疵性能評價） 對於研磨處理片數為第15片、第25片、第50片的基板，使用表面檢查裝置（科磊（KLA Tencor）公司製造，薩福斯堪（Surfscan）SP2XP）的高感度測定模式，對大小為90 nm以上的瑕疵（表面缺陷）進行檢測。對於所檢測出的各瑕疵，進行使用複查掃描式電子顯微鏡（review scanning electron microscope，review SEM）拍攝的SEM圖像的分析，測量刮痕的個數。將結果示於圖9中。 (Defect Performance Evaluation) For the 15th, 25th, and 50th substrates that have been polished, use the high-sensitivity measurement mode of a surface inspection device (manufactured by KLA Tencor, Surfscan SP2XP). Flaws (surface defects) with a size of 90 nm or more are detected. For each of the detected flaws, an analysis of a SEM image taken with a review scanning electron microscope (review SEM) was performed, and the number of scratches was measured. The results are shown in FIG. 9 .

如由圖8得知般，實施例1的研磨墊與先前公知的比較例4的研磨墊相比，階差消除速度快，且為與階差消除性能優異的比較例1的研磨墊大致相同的階差消除性能。 另外，如由圖9得知般，實施例1的研磨墊與先前公知的比較例4的研磨墊及比較例1的研磨墊相比，刮痕大幅減少，顯示出優異的瑕疵性能。 關於實施例2～實施例4，雖未圖示，但為與實施例1同等的階差消除性能、瑕疵性能。 As can be seen from FIG. 8 , the polishing pad of Example 1 has a faster level difference elimination speed than the previously known polishing pad of Comparative Example 4, and is approximately the same as the polishing pad of Comparative Example 1 having excellent level difference elimination performance. The step difference elimination performance. In addition, as can be seen from FIG. 9 , the polishing pad of Example 1 has significantly fewer scratches than the conventionally known polishing pads of Comparative Example 4 and Comparative Example 1, and exhibits excellent flaw performance. About Example 2 - Example 4, although it is not shown in figure, it is equivalent to Example 1 in level difference elimination performance, and flaw performance.

[實施方式2] （研磨層的製造） 以成為表2中記載的比例的方式，將2,4-甲苯二異氰酸酯（TDI）、高分子量多元醇混合，分別製備PP1與PP2，將其以成為表3的比例的方式混合而獲得NCO當量約520的異氰酸酯基末端胺基甲酸酯預聚物100份，於該預聚物100份中，添加混合殼部分包含丙烯腈-偏二氯乙烯共聚物、且殼內內包有異丁烷氣體的未膨脹型的中空微小球體3.5份，獲得混合液。將所獲得的混合液裝入至第一液罐中，進行保溫。其次，獨立於第一液，另行將作為硬化劑的MOCA 23.1份裝入至第二液罐中，於第二液罐內進行保溫。將第一液罐、第二液罐各自的液體以表示硬化劑中所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，自包括兩個注入口的混合機的各注入口注入至所述混合機。將注入的兩種液體一邊混合攪拌一邊注入到預熱至80℃的成形機的模具，之後，進行合模，加熱30分鐘，進行一次硬化。將一次硬化後的成形物脫模後，利用烘箱在120℃下進行4小時二次硬化，獲得胺基甲酸酯成形物。於將所獲得的胺基甲酸酯成形物放置冷卻至25℃後，再次利用烘箱於120℃下加熱5小時後切成1.3 mm的厚度，獲得研磨層8～研磨層11。 [Embodiment 2] (Manufacture of grinding layer) PP1 and PP2 were prepared by mixing 2,4-toluene diisocyanate (TDI) and a high-molecular-weight polyol so that the ratios described in Table 2 were obtained, and the NCO equivalents were obtained by mixing them in the ratios shown in Table 3. 100 parts of isocyanate group-terminated urethane prepolymer of about 520, to 100 parts of this prepolymer, add a mixed shell part containing acrylonitrile-vinylidene chloride copolymer, and isobutane is enclosed in the shell 3.5 parts of gas unexpanded hollow microspheres were used to obtain a mixed solution. The obtained mixed liquid is charged into the first liquid tank and kept warm. Next, separately from the first liquid, 23.1 parts of MOCA as a hardening agent was separately put into the second liquid tank, and kept warm in the second liquid tank. The respective liquids of the first liquid tank and the second liquid tank are self-contained in such a manner that the R value representing the equivalent ratio of the amine group and the hydroxyl group present in the curing agent to the terminal isocyanate group in the prepolymer becomes 0.90. Injection Ports Each injection port of the mixer injects into the mixer. The injected two liquids were poured into the mold of the molding machine preheated to 80°C while mixing and stirring, and then the molds were closed and heated for 30 minutes to perform primary hardening. After demoulding the primary cured molded product, secondary curing was performed in an oven at 120° C. for 4 hours to obtain a urethane molded product. After standing and cooling the obtained urethane molded product to 25° C., it was heated again in an oven at 120° C. for 5 hours, and then cut into a thickness of 1.3 mm to obtain polishing layers 8 to 11 .

（緩衝層的製造） 將包含聚酯纖維的不織布浸漬於胺基甲酸酯樹脂溶液（迪愛生（DIC）公司製造，商品名「C1367」）中。於浸漬後，使用能夠對一對輥間加壓的軋液輥，將樹脂溶液擠出，使樹脂溶液大致均勻地含浸於不織布中。繼而，藉由浸漬於包含室溫的水的凝固液中，而使含浸樹脂凝固再生，獲得樹脂含浸不織布。其後，自凝固液中取出樹脂含浸不織布，進而浸漬於包含水的清洗液中，去除樹脂中的N,N-二甲基甲醯胺（DMF）後，加以乾燥。於乾燥後，藉由拋光處理去除表面的表層，製作厚度為1.3 mm的緩衝層。 (Manufacture of buffer layer) A nonwoven fabric containing polyester fibers was dipped in a urethane resin solution (manufactured by DIC, trade name "C1367"). After impregnation, the resin solution is squeezed out using a nip roll capable of pressurizing between a pair of rolls, so that the resin solution is substantially uniformly impregnated into the nonwoven fabric. Then, the impregnated resin was coagulated and regenerated by immersing in a coagulating solution containing water at room temperature to obtain a resin-impregnated nonwoven fabric. Thereafter, the resin-impregnated nonwoven fabric was taken out from the coagulation solution, further immersed in a cleaning solution containing water, and N,N-dimethylformamide (DMF) in the resin was removed, followed by drying. After drying, the surface layer was removed by polishing to make a buffer layer with a thickness of 1.3 mm.

（實施例及比較例） 利用厚度為0.1 mm的雙面膠帶（於PET基材的兩面包括包含丙烯酸系樹脂的接著劑者）將研磨層8～研磨層11及緩衝層接合。 再者，於表2中，TDI為2,4-甲苯二異氰酸酯，PPG1000為數量平均分子量為1000的聚丙二醇，酯為使己二酸與丁二醇進行反應而獲得的數量平均分子量為1000的聚酯二醇。 (Example and Comparative Example) The polishing layer 8 to the polishing layer 11 and the buffer layer were bonded together with a 0.1 mm-thick double-sided tape (one that includes an adhesive containing an acrylic resin on both sides of the PET substrate). Furthermore, in Table 2, TDI is 2,4-toluene diisocyanate, PPG1000 is polypropylene glycol with a number average molecular weight of 1000, and ester is polypropylene glycol with a number average molecular weight of 1000 obtained by reacting adipic acid and butanediol. Polyester diol.

[表2] 異氰酸酯基末端胺基甲酸酯預聚物 當量 組成 備註 PP1 521.9 TDI/PPG1000/DEG 低硬度PPG系PP PP2 520.7 TDI/酯/DEG 低硬度聚酯系PP（酯基濃度中） TDI：2,4-甲苯二異氰酸酯 PPG1000：聚丙二醇 數量平均分子量1000 DEG：二乙二醇 酯：己二酸丁二醇系酯 分子量1000 [Table 2] Isocyanate Terminated Urethane Prepolymers equivalent composition Remark PP1 521.9 TDI/PPG1000/DEG Low hardness PPG series PP PP2 520.7 TDI/Ester/DEG Low hardness polyester PP (medium concentration of ester group) TDI: 2,4-toluene diisocyanate PPG1000: Polypropylene glycol number average molecular weight 1000 DEG: Diethylene glycol ester: Butylene adipate molecular weight 1000

[表3]    處方 PPG 調配比 PP 硬化劑 研磨層8 PP1：PP2=50：50 MOCA 50 研磨層9 PP1：PP2=30：70 30 研磨層10 PP1：PP2=100：0 100 研磨層11 PP1：PP2=0：100 0 [table 3] prescription PPG mix ratio PP hardener Grinding layer 8 PP1:PP2=50:50 MOCA 50 Grinding layer 9 PP1:PP2=30:70 30 grinding layer 10 PP1:PP2=100:0 100 Grinding layer 11 PP1:PP2=0:100 0

（脈衝NMR測定） 對於研磨層8～研磨層11，實施以下條件的脈衝NMR測定。根據弛豫時間，分為結晶相、中間相、非晶相，計算各自的比例。將結果彙總於表4及表5中。 裝置 布魯克（Bruker）公司 迷你斯派庫（Minispec）mq20（20 MHz） 核素 ¹H 測定 T ₂測定方法 固體回波（Solid echo）法 採樣規格（acquisition Scale） 0.4 msec 掃描 128次 回收延遲（Recycle Delay） 0.5 sec 測定溫度 40℃、80℃ 於裝置溫度達到測定溫度並設置試樣起60分鐘後，開始測量。試樣是使用藉由所述裝置、條件，將試樣料粒8 mmϕ約50 mg準備10片並填充至試樣管中而成者。 (Pulse NMR Measurement) For the polishing layers 8 to 11, pulse NMR measurement under the following conditions was implemented. According to the relaxation time, it is divided into crystalline phase, mesophase, and amorphous phase, and their ratios are calculated. The results are summarized in Table 4 and Table 5. Device Bruker's Minispec mq20 (20 MHz) Nuclide ¹ H Determination of T ₂ Determination method Solid echo method Sampling specification (acquisition Scale) 0.4 msec scan 128 times Recovery delay (Recycle Delay) 0.5 sec Measurement temperature 40°C, 80°C The measurement starts 60 minutes after the device temperature reaches the measurement temperature and the sample is set. The sample was prepared by preparing 10 pieces of sample material pellets 8 mmϕ about 50 mg using the above-mentioned device and conditions, and filling them into sample tubes.

[表4]    40℃ CC40 IC40 NC40 T（1） T（2） T（3） 研磨層8 37.8 36.4 25.9 0.014 0.041 0.137 研磨層9 39.5 35.1 25.4 0.014 0.042 0.153 研磨層10 32.6 37.1 30.3 0.014 0.044 0.115 研磨層11 40.6 31.8 27.6 0.014 0.042 0.179    80℃ CC80 IC80 NC80 T（1） T（2） T（3） 研磨層8 20.3 22.5 57.2 0.016 0.061 0.244 研磨層9 20.8 21.9 57.3 0.015 0.059 0.266 研磨層10 18.3 23.9 57.8 0.016 0.070 0.204 研磨層11 22.7 19.8 57.5 0.015 0.054 0.280 表4中的T（1）表示與結晶相對應的弛豫時間，T（2）表示與中間相對應的弛豫時間，T（3）表示與非晶相對應的弛豫時間。 [Table 4] 40℃ CC40 IC40 NC40 T (1) T (2) T (3) Grinding layer 8 37.8 36.4 25.9 0.014 0.041 0.137 Grinding layer 9 39.5 35.1 25.4 0.014 0.042 0.153 grinding layer 10 32.6 37.1 30.3 0.014 0.044 0.115 Grinding layer 11 40.6 31.8 27.6 0.014 0.042 0.179 80°C CC80 IC80 NC80 T (1) T (2) T (3) Grinding layer 8 20.3 22.5 57.2 0.016 0.061 0.244 Grinding layer 9 20.8 21.9 57.3 0.015 0.059 0.266 grinding layer 10 18.3 23.9 57.8 0.016 0.070 0.204 Grinding layer 11 22.7 19.8 57.5 0.015 0.054 0.280 T(1) in Table 4 indicates the relaxation time corresponding to crystallization, T(2) indicates the relaxation time corresponding to intermediate, and T(3) indicates the relaxation time corresponding to amorphous.

[表5]    NC80/CC80 NC40/CC40 （NC80/CC80）-（NC40/CC40） 研磨層8 2.8 0.7 2.1 研磨層9 2.8 0.6 2.1 研磨層10 3.2 0.9 2.2 研磨層11 2.5 0.7 1.9 [table 5] NC80/CC80 NC40/CC40 (NC80/CC80)-(NC40/CC40) Grinding layer 8 2.8 0.7 2.1 Grinding layer 9 2.8 0.6 2.1 grinding layer 10 3.2 0.9 2.2 Grinding layer 11 2.5 0.7 1.9

（研磨層及研磨墊的測定） 進行與研磨層8～研磨層11及使用研磨層8～研磨層11的實施例5至實施例6、及比較例5至比較例6的研磨墊的特性相關的測定。將結果記載於表6中。以下記述測定方法。 (Measurement of polishing layer and polishing pad) Measurements related to the properties of the polishing layers 8 to 11 and the polishing pads of Examples 5 to 6 using the polishing layers 8 to 11 , and Comparative Examples 5 to 6 were performed. The results are described in Table 6. The measurement method is described below.

[表6]    使用 研磨層 密度 D硬度 R值 HS距離 （nm） 透過率 峰值時 的Q值 評價 磨耗性 階差 瑕疵 實施例5 研磨層8 0.82 46.5 0.90 7.9 0.223 0.799 ○ ○ ○ 實施例6 研磨層9 0.80 45.5 0.90 8.4 0.240 0.750 ○ ○ ○ 比較例5 研磨層10 0.84 49.5 0.90 9.9 0.216 0.633 × ○ ○ 比較例6 研磨層11 0.81 45.0 0.90 10.0 0.216 0.627 ○ × × [Table 6] use abrasive layer density D hardness R value HS distance (nm) Transmittance Q value at peak evaluate Abrasive step difference flaw Example 5 Grinding layer 8 0.82 46.5 0.90 7.9 0.223 0.799 ○ ○ ○ Example 6 Grinding layer 9 0.80 45.5 0.90 8.4 0.240 0.750 ○ ○ ○ Comparative Example 5 grinding layer 10 0.84 49.5 0.90 9.9 0.216 0.633 x ○ ○ Comparative example 6 Grinding layer 11 0.81 45.0 0.90 10.0 0.216 0.627 ○ x x

（硬鏈段的距離） 基於所述說明的內容，藉由以下測定條件測定研磨層8～研磨層11的硬鏈段的距離。 [測定條件] 裝置                      ：BL8S3（愛知同步加速輻射中心（Aichi Synchrotron Radiation center）） 波長                      ：1.5埃 測定檢測器            ：R-AXIS IV++ 測定時間               ：120 sec 測定相機長度        ：3976.88 mm 將研磨層8（實施例5）與研磨層10（比較例5）的測定資料示於圖3、圖4、圖5中。將由資料獲得的硬鏈段的距離（HS距離）、此時的峰值時的Q的值、以及透過率示於表3中。 (distance of hard segment) Based on the content of the above description, the distance of the hard segment of the polishing layer 8 to the polishing layer 11 was measured under the following measurement conditions. [measurement conditions] Installation : BL8S3 (Aichi Synchrotron Radiation center) Wavelength : 1.5 Angstroms Determination detector : R-AXIS IV++ Measuring time : 120 sec Measuring camera length : 3976.88 mm The measurement data of the polishing layer 8 (Example 5) and the polishing layer 10 (Comparative Example 5) are shown in FIG. 3 , FIG. 4 , and FIG. 5 . Table 3 shows the distance of the hard segment (HS distance), the value of Q at the peak at this time, and the transmittance obtained from the data.

（密度） 研磨層的密度（g/cm ³）是依據日本工業標準（JIS K 6505）進行測定。 (Density) The density (g/cm ³ ) of the polishing layer was measured in accordance with Japanese Industrial Standards (JIS K 6505).

（D硬度） 研磨層的D硬度是依據日本工業標準（JIS-K-6253），使用D型硬度計進行測定。此處，測定試樣是藉由以至少總厚度成為4.5 mm以上的方式根據需要將多片研磨層重疊而獲得。 (D hardness) The D hardness of the abrasive layer was measured using a D-type hardness tester in accordance with Japanese Industrial Standards (JIS-K-6253). Here, the measurement sample is obtained by laminating a plurality of polishing layers as needed so that at least the total thickness becomes 4.5 mm or more.

（磨耗試驗） 對於所獲得的研磨墊，使用小型摩擦磨耗試驗機，於下述條件下進行磨耗試驗。於所獲得的磨耗試驗結果中，表6中在0.15 mm以下時表述為○，在超過0.15 mm時表述為×。 (wear test) The obtained polishing pad was subjected to an abrasion test under the following conditions using a small friction and abrasion tester. In the obtained wear test results, in Table 6, when it is less than 0.15 mm, it is expressed as ○, and when it exceeds 0.15 mm, it is expressed as ×.

（磨耗試驗條件） 使用研磨機：小型摩擦磨耗試驗機 壓頭側：PAD（17ϕ） 壓盤側：#180砂紙 載荷：300 g 液體：水 流量：45 ml/分鐘 壓盤轉數：40 rpm 時間：10分鐘 厚度測定載荷：300 g (Abrasion test conditions) Grinding machine used: small friction and wear testing machine Indenter side: PAD (17ϕ) Platen side: #180 sandpaper Load: 300g liquid: water Flow rate: 45 ml/min Platen revolutions: 40 rpm Time: 10 minutes Thickness measurement load: 300 g

為適當的硬鏈段距離的實施例5至實施例6顯示出優異的磨耗性能，但於使用異氰酸酯末端預聚物中的高分子量多元醇僅為PPG或僅酯的研磨層的比較例5至比較例6中，並非良好的結果。Examples 5 to 6 with an appropriate hard segment distance show excellent abrasion performance, but comparative examples 5 to 6 in which the high molecular weight polyol in the isocyanate-terminated prepolymer is only PPG or only ester is used in the abrasive layer. In Comparative Example 6, it was not a good result.

使用所獲得的實施例5至實施例6、比較例5至比較例6的研磨墊，於下述研磨條件下進行研磨試驗，評價研磨性能（階差消除性能及瑕疵性能）。 （研磨條件） 使用研磨機：F-REX300X（荏原製作所公司製造） 盤（Disk）：A188（3M公司製造） 研磨劑溫度：20℃ 研磨壓盤轉數：85 rpm 研磨頭轉數：86 rpm 研磨壓力：3.5 psi 研磨漿料（金屬膜）：CSL-9044C（使用CSL-9044C原液：純水=重量比1：9的混合液）（福吉米公司（Fujimi Corporation）製造） 研磨漿料流量：200 ml/min 研磨時間：60秒 被研磨物（金屬膜）：Cu膜基板 墊磨合：35 N 10分鐘 調節：異位（Ex-situ）、35 N、4次掃描 Using the obtained polishing pads of Examples 5 to 6 and Comparative Examples 5 to 6, a polishing test was performed under the following polishing conditions to evaluate polishing performance (level difference elimination performance and flaw performance). (grinding condition) Grinder used: F-REX300X (manufactured by Ebara Seisakusho) Disk (Disk): A188 (manufactured by 3M Company) Abrasive temperature: 20°C Grinding platen revolutions: 85 rpm Grinding head rotation speed: 86 rpm Grinding Pressure: 3.5 psi Polishing slurry (metal film): CSL-9044C (use CSL-9044C stock solution: pure water = mixed solution with a weight ratio of 1:9) (manufactured by Fujimi Corporation) Grinding slurry flow: 200 ml/min Grinding time: 60 seconds Object to be polished (metal film): Cu film substrate Pad break-in: 35 N for 10 minutes Conditioning: Ex-situ, 35 N, 4 scans

（階差消除性能試驗） 將研磨墊經由具有丙烯酸系接著劑的雙面膠帶而設置於研磨裝置的規定位置，於所述研磨條件下實施研磨加工。階差消除性能是藉由利用階差/表面粗糙度/微細形狀測定裝置（科磊（KLA Tencor）公司製造，P-16+）對120 μm/120 μm、100 μm/100 μm、50 μm/50 μm、10 μm/10 μm的各配線寬度的凹陷進行測定來評價。 對於具有7000埃的膜厚、3000埃的階差的圖案晶圓，以一次研磨量成為1000埃的方式調整研磨速率，並實施研磨，階段性地進行研磨，每次實施晶圓的階差測定。於所有的配線寬度中，將研磨量為6000埃以下時階差消除者表述為○，將研磨量超過6000埃後消除者或者階差未消除者表述為×。 (Stand difference elimination performance test) A polishing pad was installed at a predetermined position of a polishing apparatus through a double-sided tape having an acrylic adhesive, and polishing was performed under the above-mentioned polishing conditions. The step elimination performance is determined by using a step/surface roughness/micro shape measuring device (manufactured by KLA Tencor, P-16+) for 120 μm/120 μm, 100 μm/100 μm, 50 μm/ The dishing of each wiring width of 50 μm and 10 μm/10 μm was measured and evaluated. For a patterned wafer having a film thickness of 7000 angstroms and a step difference of 3000 angstroms, the polishing rate was adjusted so that the amount of polishing at one time became 1000 angstroms, and polishing was performed in stages, and the level difference measurement of the wafer was performed each time . In all the wiring widths, the level difference was eliminated when the polishing amount was less than 6000 angstroms, and the level difference was eliminated when the polishing amount exceeded 6000 angstroms, or the level difference was not eliminated.

（瑕疵性能評價） 對於研磨處理片數為第16片、第26片、第51片的基板，使用表面檢查裝置（科磊（KLA Tencor）公司製造，薩福斯堪（Surfscan）SP2XP）的高感度測定模式，對大小為155 nm以上的瑕疵（表面缺陷）進行檢測。對於所檢測出的各瑕疵，進行使用複查SEM拍攝的SEM圖像的分析，測量刮痕的個數。若為實際業務上認為必要的10個以下的刮痕數，則表述為○，若為超過10個的刮痕數，則表述為×。 [產業上的可利用性] (Defect Performance Evaluation) For the 16th, 26th, and 51st substrates that have been polished, use the high-sensitivity measurement mode of a surface inspection device (manufactured by KLA Tencor, Surfscan SP2XP). Flaws (surface defects) with a size of 155 nm or more are detected. For each flaw detected, the analysis of the SEM image image|photographed by the review SEM was performed, and the number of objects of scratches was measured. If the number of scratches is 10 or less which is considered necessary in actual business, it is expressed as ◯, and if the number of scratches exceeds 10, it is expressed as ×. [industrial availability]

本發明有助於研磨墊的製造、銷售，因此具有產業上的可利用性。Since the present invention contributes to the manufacture and sale of polishing pads, it has industrial applicability.

1:研磨裝置 3:研磨墊 4:研磨層 4A:中空微小球體 6:緩衝層 7:接著層 8:被研磨物 9:漿料 10:研磨壓盤 16:保持壓盤 1: Grinding device 3: Grinding pad 4: Grinding layer 4A: Hollow microspheres 6: buffer layer 7: Next layer 8: Grinding object 9: Slurry 10: Grinding platen 16: Hold the pressure plate

圖1是研磨裝置1的立體圖。 圖2的（a）、圖2的（b）是研磨墊的剖面圖。 圖3是實施例5及比較例5的研磨墊的各自的研磨層的利用X射線小角散射法獲得的測定結果。 圖4是圖3的所畫圈周邊的放大圖。 圖5是以容易求出極大值的方式對圖4的圖表進行修正而成的圖。 圖6的（a）～圖6的（c）是表示階差研磨量試驗中的階差狀態的示意圖的圖。 圖7是表示實施例及比較例的研磨墊的磨耗量（厚度）的變化的圖表。 圖8是實施例及比較例的階差消除性能的試驗結果。 圖9是實施例及比較例的瑕疵性能的研磨試驗結果。 FIG. 1 is a perspective view of a polishing device 1 . FIG. 2( a ) and FIG. 2( b ) are cross-sectional views of polishing pads. 3 is the measurement results obtained by the X-ray small-angle scattering method of the respective polishing layers of the polishing pads of Example 5 and Comparative Example 5. FIG. FIG. 4 is an enlarged view around the circle drawn in FIG. 3 . FIG. 5 is a diagram obtained by correcting the graph in FIG. 4 so that the maximum value can be easily obtained. 6( a ) to 6( c ) are diagrams showing schematic diagrams of the state of the level difference in the level difference grinding amount test. 7 is a graph showing changes in the amount of abrasion (thickness) of polishing pads of Examples and Comparative Examples. Fig. 8 shows the test results of the level difference canceling performance of Examples and Comparative Examples. FIG. 9 shows the results of polishing tests of flaw performance in Examples and Comparative Examples.

1:研磨裝置 1: Grinding device

3:研磨墊 3: Grinding pad

4:研磨層 4: Grinding layer

6:緩衝層 6: buffer layer

8:被研磨物 8: Grinding object

9:漿料 9: Slurry

10:研磨壓盤 10: Grinding platen

16:保持壓盤 16: Hold the pressure plate

Claims (22)

一種研磨墊，具有包含聚胺基甲酸酯樹脂發泡體的研磨層，所述聚胺基甲酸酯樹脂發泡體源自異氰酸酯末端預聚物及硬化劑，所述研磨墊中， 藉由X射線小角散射法測定的所述研磨層中的硬鏈段間的距離為9.5 nm以下。 A polishing pad having a polishing layer comprising a polyurethane resin foam derived from an isocyanate-terminated prepolymer and a hardener, in the polishing pad, The distance between the hard segments in the polishing layer measured by X-ray small-angle scattering method is 9.5 nm or less. 如請求項1所述的研磨墊，其中所述異氰酸酯末端預聚物包含源自聚異氰酸酯化合物的構成單元、與源自高分子量多元醇的構成單元， 所述源自高分子量多元醇的構成單元至少包含聚丙二醇構成單元、與聚酯二醇構成單元。 The polishing pad according to claim 1, wherein the isocyanate-terminated prepolymer comprises a structural unit derived from a polyisocyanate compound and a structural unit derived from a high molecular weight polyol, The structural unit derived from the high molecular weight polyol includes at least a polypropylene glycol structural unit and a polyester diol structural unit. 如請求項2所述的研磨墊，其中相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元小於60重量%。The polishing pad according to claim 2, wherein the polypropylene glycol constituting unit is less than 60% by weight relative to the constituting unit derived from a high molecular weight polyol. 如請求項2所述的研磨墊，其中用於形成所述聚酯二醇構成單元的聚酯二醇為600～2500的數量平均分子量。The polishing pad according to claim 2, wherein the polyester diol used to form the polyester diol constituent unit has a number average molecular weight of 600-2500. 如請求項1所述的研磨墊，其中所述聚胺基甲酸酯樹脂發泡體的平均氣泡徑為5 μm以上且小於20 μm。The polishing pad according to claim 1, wherein the polyurethane resin foam has an average cell diameter of 5 μm or more and less than 20 μm. 如請求項1所述的研磨墊，其中所述異氰酸酯末端預聚物的NCO當量為500～600。The polishing pad according to claim 1, wherein the NCO equivalent weight of the isocyanate-terminated prepolymer is 500-600. 如請求項1所述的研磨墊，其中藉由X射線小角散射法測定的所述研磨層中的硬鏈段間的距離為3.0 nm～9.5 nm。The polishing pad according to claim 1, wherein the distance between hard segments in the polishing layer measured by X-ray small-angle scattering method is 3.0 nm to 9.5 nm. 一種研磨墊的製造方法，製造具有包含聚胺基甲酸酯樹脂發泡體的研磨層的研磨墊，所述製造方法包括： 將異氰酸酯末端預聚物與硬化劑混合並進行反應，從而獲得所述聚胺基甲酸酯樹脂發泡體的步驟；以及 將所述聚胺基甲酸酯樹脂發泡體成形並製成研磨層的形狀的步驟，並且 藉由X射線小角散射法測定的所述研磨層中的硬鏈段間的距離為9.5 nm以下。 A kind of manufacture method of polishing pad, manufacture has the polishing pad that comprises the polishing layer of polyurethane resin foam, and described manufacturing method comprises: a step of mixing and reacting an isocyanate-terminated prepolymer and a hardener to obtain the polyurethane resin foam; and a step of shaping the polyurethane resin foam into the shape of an abrasive layer, and The distance between the hard segments in the polishing layer measured by X-ray small-angle scattering method is 9.5 nm or less. 如請求項8所述的研磨墊的製造方法，其中於將異氰酸酯末端預聚物與硬化劑混合時，亦使未膨脹氣球共存。The method of manufacturing a polishing pad according to claim 8, wherein when the isocyanate-terminated prepolymer and the hardener are mixed, unexpanded balloons are also allowed to coexist. 一種研磨墊，具有包含聚胺基甲酸酯樹脂發泡體的研磨層，所述聚胺基甲酸酯樹脂發泡體源自異氰酸酯末端預聚物及硬化劑，所述研磨墊中， 藉由脈衝核磁共振法於80℃下所測定的所述研磨層中的非晶相的含有重量比例（NC80）相對於藉由脈衝核磁共振法於80℃下所測定的所述研磨層中的結晶相的含有重量比例（CC80）的比（NC80/CC80）為2.6～3.1， 藉由脈衝核磁共振法於40℃下所測定的所述研磨層中的非晶相的含有重量比例（NC40）相對於藉由脈衝核磁共振法於40℃下所測定的所述研磨層中的結晶相的含有重量比例（CC40）的比（NC40/CC40）為0.5～0.9。 A polishing pad having a polishing layer comprising a polyurethane resin foam derived from an isocyanate-terminated prepolymer and a hardener, in the polishing pad, The content ratio (NC80) of the amorphous phase in the polishing layer measured at 80°C by the pulse nuclear magnetic resonance method is compared to the content ratio of the amorphous phase in the polishing layer measured at 80°C by the pulse nuclear magnetic resonance method The ratio (NC80/CC80) of the weight ratio (CC80) of the crystalline phase is 2.6 to 3.1, The ratio by weight (NC40) of the amorphous phase in the polishing layer measured at 40°C by pulse nuclear magnetic resonance to the content of the amorphous phase in the polishing layer measured at 40°C by pulse nuclear magnetic resonance The ratio (NC40/CC40) of the content ratio (CC40) of the crystal phase is 0.5-0.9. 如請求項10所述的研磨墊，其中由下述式（1）獲得的數值大於1.9且小於2.2， [數式1] （NC80/CC80）-（NC40/CC40）  ･･･（1）。 The polishing pad according to claim 10, wherein the value obtained by the following formula (1) is greater than 1.9 and less than 2.2, [Formula 1] (NC80/CC80)-(NC40/CC40) ･･･(1). 如請求項10所述的研磨墊，其中所述CC80為19.0重量%～22.0重量%。The polishing pad according to claim 10, wherein the CC80 is 19.0% by weight to 22.0% by weight. 如請求項10所述的研磨墊，其中所述NC40為22.0重量%～27.0重量%。The polishing pad according to claim 10, wherein the NC40 is 22.0% by weight to 27.0% by weight. 如請求項10所述的研磨墊，其中所述異氰酸酯末端預聚物包含源自聚異氰酸酯化合物的構成單元、與源自高分子量多元醇的構成單元， 所述源自高分子量多元醇的構成單元至少包含聚丙二醇構成單元、與聚酯二醇構成單元。 The polishing pad according to claim 10, wherein the isocyanate-terminated prepolymer comprises a structural unit derived from a polyisocyanate compound and a structural unit derived from a high molecular weight polyol, The structural unit derived from the high molecular weight polyol includes at least a polypropylene glycol structural unit and a polyester diol structural unit. 如請求項14所述的研磨墊，其中相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元小於60重量%。The polishing pad according to claim 14, wherein the polypropylene glycol constituting unit is less than 60% by weight relative to the constituting unit derived from a high molecular weight polyol. 如請求項14或請求項15所述的研磨墊，其中用於形成所述聚酯二醇構成單元的聚酯二醇為600～2500的數量平均分子量。The polishing pad according to claim 14 or claim 15, wherein the polyester diol used to form the polyester diol constituent unit has a number average molecular weight of 600-2500. 如請求項10所述的研磨墊，其中所述異氰酸酯末端預聚物的NCO當量為500～600。The polishing pad according to claim 10, wherein the NCO equivalent of the isocyanate-terminated prepolymer is 500-600. 一種研磨墊的製造方法，製造具有包含聚胺基甲酸酯樹脂發泡體的研磨層的研磨墊，所述製造方法包括： 將異氰酸酯末端預聚物與硬化劑混合並進行反應，從而獲得所述聚胺基甲酸酯樹脂發泡體的步驟；以及 將所述聚胺基甲酸酯樹脂發泡體成形並製成研磨層的形狀的步驟，並且 藉由脈衝核磁共振法於80℃下所測定的所述研磨層中的非晶相的含有重量比例（NC80）相對於藉由脈衝核磁共振法於80℃下所測定的所述研磨層中的結晶相的含有重量比例（CC80）的比（NC80/CC80）為2.6～3.1， 藉由脈衝核磁共振法於40℃下所測定的所述研磨層中的非晶相的含有重量比例（NC40）相對於在40℃下所測定的所述研磨層中的結晶相的含有重量比例（CC40）的比（NC40/CC40）為0.5～0.9。 A kind of manufacture method of polishing pad, manufacture has the polishing pad that comprises the polishing layer of polyurethane resin foam, and described manufacturing method comprises: a step of mixing and reacting an isocyanate-terminated prepolymer and a hardener to obtain the polyurethane resin foam; and a step of shaping the polyurethane resin foam into the shape of an abrasive layer, and The content ratio (NC80) of the amorphous phase in the polishing layer measured at 80°C by the pulse nuclear magnetic resonance method is compared to the content ratio of the amorphous phase in the polishing layer measured at 80°C by the pulse nuclear magnetic resonance method The ratio (NC80/CC80) of the weight ratio (CC80) of the crystalline phase is 2.6 to 3.1, The weight ratio of the amorphous phase in the polishing layer measured at 40°C by pulse nuclear magnetic resonance (NC40) to the weight ratio of the crystalline phase in the polishing layer measured at 40°C The ratio (NC40/CC40) of (CC40) is 0.5-0.9. 一種研磨墊，具有包含聚胺基甲酸酯樹脂發泡體的研磨層，所述聚胺基甲酸酯樹脂發泡體源自異氰酸酯末端預聚物及硬化劑，所述研磨墊中， 所述異氰酸酯末端預聚物包含源自聚異氰酸酯化合物的構成單元、與源自高分子量多元醇的構成單元， 所述源自高分子量多元醇的構成單元至少包含聚丙二醇構成單元、與聚酯二醇構成單元， 相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元小於60重量%。 A polishing pad having a polishing layer comprising a polyurethane resin foam derived from an isocyanate-terminated prepolymer and a hardener, in the polishing pad, The isocyanate-terminated prepolymer includes a structural unit derived from a polyisocyanate compound and a structural unit derived from a high-molecular-weight polyol, The structural units derived from high molecular weight polyols include at least polypropylene glycol structural units and polyester diol structural units, The polypropylene glycol constituent unit is less than 60% by weight relative to the constituent unit derived from the high molecular weight polyol. 如請求項19所述的研磨墊，其中相對於所述源自高分子量多元醇的構成單元，所述聚丙二醇構成單元為30重量%～50重量%。The polishing pad according to claim 19, wherein the constituent unit of polypropylene glycol is 30% by weight to 50% by weight relative to the constituent unit derived from high molecular weight polyol. 如請求項19或請求項20所述的研磨墊，其中所述聚酯二醇構成單元源自具有600～2500的數量平均分子量的聚酯二醇。The polishing pad according to claim 19 or claim 20, wherein the polyester diol constituting unit is derived from a polyester diol having a number average molecular weight of 600-2500. 一種製造方法，製造具有包含聚胺基甲酸酯樹脂發泡體的研磨層的研磨墊，所述製造方法包括： 使聚異氰酸酯化合物、與至少包含聚丙二醇及聚酯二醇的高分子量多元醇進行反應，從而獲得異氰酸酯末端預聚物的步驟； 使所述異氰酸酯末端預聚物與硬化劑進行反應，從而獲得所述聚胺基甲酸酯樹脂發泡體的步驟；以及 將所述聚胺基甲酸酯樹脂發泡體成形並製成研磨層的形狀的步驟，並且 相對於所述高分子量多元醇總量，所述聚丙二醇小於60重量%。 A kind of manufacturing method, manufacture has the polishing pad that comprises the abrasive layer of polyurethane resin foam, and described manufacturing method comprises: A step of reacting polyisocyanate compounds with high molecular weight polyols comprising at least polypropylene glycol and polyester diol to obtain an isocyanate-terminated prepolymer; reacting the isocyanate-terminated prepolymer with a hardener to obtain the polyurethane resin foam; and a step of shaping the polyurethane resin foam into the shape of an abrasive layer, and The polypropylene glycol is less than 60% by weight relative to the total amount of the high molecular weight polyol.

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