TWI222390B - Polishing pad and its production method - Google Patents

Abstract

A polishing pad whereby optical material for lenses, reflecting mirrors and the like, or a work material requiring a high degree of surface flatness, as in the polishing of glass substrates or aluminum substrates for silicone wafers and hard disks, or general metal polishing, can be flattened with stability and high polishing efficiency. Further, a polishing pad for semiconductor wafers is provided that is superior in flattening characteristic and free from scratches and that can be produced at low cost. A polishing pad is provided that is free from de-chucking error so that neither damages to wafers nor decrease in operating efficiency occurs. A polishing pad is provided that is satisfactory in flatness, in-plane uniformity, and polishing speed and that produces less change in polishing speed. A polishing pad is provided that can make planarity improvement and scratch reduction compatible.

Description

1222390 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings are briefly explained) L The technical field to which the invention belongs 3 TECHNICAL FIELD The present invention relates to a lens that can Optical materials such as mirrors, or polishing pads that require high surface flatness, such as materials that require high surface flatness, such as five-stone wafers, glass substrates for hard disks, substrates, and general metal polishing processes. The polishing pad of the present invention can also be used in a planarization process, in particular, a silicon wafer and a device having an oxide layer, a metal layer, etc. formed thereon are further processed before being laminated and forming such oxide layers or metal layers. Ping 10 Tanned Procedure. The present invention also relates to a method for manufacturing the aforementioned polishing pad. I: Prior art 3 Technical background For materials requiring a high level of surface flatness, a single crystal silicon disk called a silicon wafer, which is used to manufacture semiconductor volumetric circuits (IC, LSI), can be used as an example. In the manufacturing process of IC, LSI, etc., in order to form a reliable semiconductor bond for various thin films used in circuit formation, silicon wafers are required to have a high level of surface in each process for laminating and forming an oxide layer or a metal layer. Precision processing to make it flat. In such a grinding and polishing process, generally speaking, the polishing pad is fixed on a rotatable 20 support disk called a platen, and processed objects such as semiconductor wafers are fixed on the polishing pad. Then, the relative speed between the polishing platform and the polishing pad is generated by the movements of both sides, and then a slurry containing abrasive particles is continuously supplied on the polishing pad to perform the polishing operation. A chemical mechanical polishing apparatus (8 1222390 玖, description of the invention CMP apparatus) for flattening the working surface by the CMP method is shown in FIG. 1 and described here. The CMP apparatus used by the CMP method has a polishing turntable 2 to support a polishing pad 1, and a bearing table (polishing head) 4 to support a material to be polished (wafer) 3. The polishing turntable 2 and the supporting table 4 are arranged such that the polishing pads 1 and 5 supported by them and the object 3 to be polished face each other, and are configured to be rotatable with the rotating shafts 6 and 7 as the center. The material to be polished 3 is adhered to the supporting table 4 and is provided with a pressing mechanism for pressing the material to be polished 3 on the polishing pad 1 during grinding. The abrasive supply mechanism 5 is used to supply a slurry containing abrasive particles such as silicon dioxide particles in an alkaline solution to a polishing pad 1 on a polishing pad 2. In this way, the semiconductor wafer is subjected to a mirror polishing or a planarization of an interlayer insulating film or a conductive film by a so-called Chemical Mechanical Polishing method during a multi-layer wiring process of a process or a device. These polishing requirements are based on the uniformity of the polishing amount throughout the wafer 15, the selective polishing of the convex portions in the unevenness of the unevenness, or the flatness of the uneven portions after polishing. For these requirements, the grinding pads of the following structures are developed and reviewed in the past and are well known. (1) Laminated synthetic leather layer with abrasive layer on elastic polyurethane layer (US Patent No. 3,504,457) 20 (2) Adhesive impregnated polyamine on foamed polyurethane layer Non-woven fabrics of acetic acid esters (Japanese Patent Laid-Open Publication No. 6-21028) (3) —A polishing pad provided with a polishing surface, and a rigid element with a selected thickness and rigidity is provided adjacent to the polishing surface, and adjacent to each other The rigid element is provided with an elastic element to impart substantially the same force to the rigid element, and the rigidity is 9 玖. The invention element and the elastic element impart elastic f to the polishing surface, which results in a controllable 1 curve of the polishing surface, making it suitable. Add 1 to the overall shape of the surface and maintain the rigidity that can control the local shape of the surface of the processed object (Japanese Patent Laid-Open Publication No. 6-077185) (4) An abrasive cloth, which has a Young's modulus ^ A large surface layer A and a lower layer B below the Young's modulus, and an intermediate layer M having at least a Young's modulus larger than the aforementioned B layer is provided between the two layers a and B (refer to Japanese Patent Laid-Open Publication No. 10- No. 156724) (5) —species research Layer, the polishing layer is higher than the elastic intermediate layer, the bottom layer of soft configuration, the gasket and the division of the intermediate layer (Japanese Laid-Open Patent Publication No. 11 -48131), but 'the polishing pad, there are various problems as follows. (a) The polishing pads described in U.S. Patent Nos. 3,504 and 457, in terms of overall uniformity, can achieve the effect of balancing the load of the flexible polyurethane layer applied to the wafer. Synthetic leather is free of problems such as scratches, but has poor flatness characteristics in micro fields. (b) The polishing pad described in Japanese Patent Laid-Open Publication No. 6-21028. The non-woven fabric layer can achieve the same effect as the elastic polyurethane layer of the polishing pad described in US Patent No. 3,504,457. And obtain uniformity. In addition, the abrasive layer also has a rigid foamed polyurethane layer, so the planarization characteristics are also better than synthetic leather. However, in recent years, it has not been able to respond to the improvement of the level of planarization characteristics required in micro-fields. It did not reach the required grade on grinding. By increasing the thickness of the hard urethane layer, although the effect of improving the planarization characteristics can be achieved, it will cause more scratches instead of _ 1222390 发明, a practical method of invention description. U) The polishing pad described in Japanese Patent Laid-Open Publication No. 6-77185 has an appropriate hardness that keeps the polishing layer of the surface layer free of scratches, and flatness characteristics in the second layer because the hardness does not increase. The rigid layer can be changed by the 5 good constructers. This is to solve the problems of the polishing pads described in Japanese Patent Laid-Open Publication No. 6-21028, but the thickness of the polishing layer is limited to 0.003㈣τ, which is actually made _ even the polishing layer is also ground. There are shortcomings of short products. (d) The basic idea of polishing 10 pads described in Japanese Patent Laid-Open Publication No. 1G-156724 is the same as the technology of Japanese Patent Laid-Open Publication No. 6_77185, which limits the elastic modulus range of each layer to obtain a more efficient one. Range, but this technology does not actually record any mechanism for implementation, so it is really difficult to make polishing pads. (e) The polishing pad of Japanese Patent Laid-Open Publication No. u_4813l has the same basic idea as that of Japanese Patent Laid-Open Publication No. 6-77185, and has an intermediate rigid layer in order to further improve the uniformity within the wafer surface. Split into a certain pre-size. However, according to this technology, the segmentation process requires a cost ′ and cannot provide an inexpensive polishing pad. Also, the polishing pads already included in the § 4 special literature are generally bonded to the polishing machine with an adhesive such as double-sided tape 20 tape, but the bonding strength at this time has never been reviewed. . Moreover, in the grinding pads which are generally used nowadays, when the polishing pad is peeled from the grinder after use, a very large amount of force is required ', which makes the reattachment of the polishing pad extremely labor-intensive. The present invention is a polishing pad used in a polishing process for flattening the minute irregularities of a pattern of a device having a fine pattern formed on a semiconductor wafer or even a semiconductor wafer 11 1222390 玖, and provides a polishing method for polishing. It has a polishing pad with a high polishing rate and a polishing method for a semiconductor wafer. In addition, a polishing pad for a semiconductor wafer with a fine pattern formed on the semiconductor wafer during polishing is provided, which has good planarization characteristics, has no scratches, and can be manufactured at low cost. A method for polishing semiconductor wafers. Also, in the polishing operation, the size change of the polishing pad is very important. If the size stability of the polishing pad is poor, the frictional heat generated during the polishing process will change the size of the polishing pad by 10, and will cause the flatness characteristics to decrease. In the past, within the polishing characteristics, the flatness of the polishing object was improved. For the purpose of (planarity), most of the polishing pads have high elastic modulus, but the dimension stability of the polishing pads has not been discussed well. 15 Another object of the present invention is to provide a polishing layer having a flatness characteristic that is lower than that of a conventional polishing pad when the temperature rises due to frictional heat generated during the polishing process. The polishing pad used in the high-precision polishing is generally a polyurethane foam sheet having a void ratio of about 30% to 35%. 20 In addition, it is important for the polishing pad to finish the polishing in a short time as possible, so a high polishing rate is required for the polishing pad. However, when the conventional polyurethane foam sheet is used as the polishing pad or even the polishing layer of the polishing pad, although the polishing efficiency can be improved by improving the polishing rate, the resistance changes when the wafer is removed from the polishing pad after polishing. It is large, and there is a problem that 12 V 1222390 玖, the so-called dechuck error of the invention description, damage to the wafer, and reduction in operating efficiency are caused. Another object of the present invention is to provide a method that can maintain a high polishing rate, and reduces the resistance when the wafer is removed from the polishing pad after the polishing is completed without the occurrence of an unclamping error. Therefore, the wafer is not damaged and the operating efficiency is not reduced. The polishing pad and even the polishing layer of the polishing pad.

In addition, the polishing characteristics of the polishing pad require planarity, planarity, and polishing speed of the object to be polished. In terms of flatness and in-plane uniformity of the object to be polished, it can be improved to a certain degree by making the polishing layer highly elastic. In addition, the polishing speed can be increased by forming a bubble containing foam. However, if the polishing speed varies between the start of use and the end of use, the polishing conditions cannot be adjusted, resulting in poor polishing efficiency. Another object of the present invention is to provide a flatness, uniformity within the surface, and polishing. A polishing pad with good speed and little change in polishing speed.

The polishing pads used in such CMP processes are known in Japanese Patent Gazette No. 3013105 and Patent Publication Gazette No. 11-322878. The technique disclosed in Japanese Patent Gazette No. 3013105 is a polishing pad in which fine particles of water-soluble resin 20 or even hollow fine particles are added to a polymer matrix such as a polyurethane polymer. In addition, the technique disclosed in Japanese Patent Laid-Open Publication No. 11-322878 is a polishing pad in which polystyrene foam beads are dispersed in a polyurethane polymer. However, when the aforementioned known polishing pad disperses water-soluble resin particles or even hollow particles or polystyrene foam beads in the resin, it is because of its interaction with the matrix tree 13 1222390 玖, the polyurethane of the invention description fat. The density is poor, and uneven particles are likely to occur. The fine particles and even the hollow fine particles in the aforesaid known technology are used to form small recesses on the polishing surface of the polishing pad during CMP processing and to maintain the important function of the abrasive particles. 5 The performance of the polishing pad has a great impact. In addition, you may use a polyurethane foam containing an isoramic acid ester-containing compound to react with an active hydrogen group-containing compound and harden it to make a polishing pad. In some cases, even if the same constituents are used, sufficient polishing performance may not be obtained. Therefore, it is necessary to seek improvement. 10 Another object of the present invention is to provide a polishing pad manufacturing method having a polishing layer made of foamed polyurethane and having stable polishing characteristics, and to provide a water-free resin particle or even a hollow particle, Or a method of manufacturing a polishing pad, such as a material such as polyethylene foam beads, which forms a recess on the polishing surface, and has a polishing pad whose pores are only made of polyurethane. 15 During this polishing operation, heat is generated due to friction between the polishing pad and the workpiece, which causes the surface temperature of the polishing pad to rise. As the temperature rises, the hardness (elastic modulus) of the polishing pad changes, which adversely affects the flattening process that requires a high degree of surface flatness. Another object of the present invention is to provide a conventional problem that can overcome the change in hardness (elastic modulus) of the polishing pad caused by the frictional heat between the polishing pad and the workpiece during polishing, and cause a bad influence on the flattening process. , And can be stable in a large temperature range for flattening grinding 塾. In addition, the polishing pad used for high-precision polishing is described in Japanese Patent Publication No. 3013105, dispersed in a matrix resin such as polyurethane 14 1222390 发明, and the invention describes a hollow microsphere containing a high M gas. Abrasive pads (made by Rodei). However, the most widely known abrasive pads containing hollow microspheres containing high-pressure gas are not widely known as flatness. Claim. Book collection: Tomi Toro is waiting for "Detailed Semiconductor CMP Technology 5" Industrial Survey Meeting, page 17 (2000). If you consider the expansion of the new generation of components, Muramura will improve the flatness of the hard grinding. pad. For the purpose of improving the flatness, a non-foamed hard polishing pad (for example, a product name of Rodale Co., Ltd .: Ic_2000) may be used. However, it is also described in the aforementioned collection of books (same page as above) that the use of this hard grinding trowel may cause scratches (scratches) on the polished surface of the object to be processed. In addition, the non-foaming polishing pad cannot sufficiently maintain the abrasive particles in the polishing liquid on the surface of the polishing pad during the polishing operation, so it is not ideal from the viewpoint of the polishing speed. 15 In addition, Japanese Patent Laid-Open Publication No. 2001-47355 proposes a polishing pad in which a water-soluble substance is dispersed in a water-insoluble thermoplastic polymer. Although the polishing pad is non-foamed, the water-soluble substance dispersed in the polishing pad will dissolve during polishing and form a foam-like hole on the surface of the polishing pad. The surface of the polishing pad will be caused by the swelling of the polishing pad. Since the hardness is reduced, it is very effective in improving flatness of 20 liters and improving polishing speed. However, the characteristics of the polishing pad are very large in terms of the effect exerted by the water-soluble substance, but it cannot solve the scratches caused by the thermoplastic polymer mainly used to form the polishing pad. Another object of the present invention is to provide a Among the conventional polishing pads, 15%, the description of the invention fails to coexist, and can simultaneously achieve an improvement in flatness and a reduction in scratches. Furthermore, the present invention further provides a polishing pad which can achieve flatness and reduce scratches, and can also meet the requirements from the viewpoint of polishing speed. In addition, in the polishing operation, the wettability of the polishing pad to the polishing liquid is very important. If the wettability of the polishing pad to the polishing liquid is poor, the polishing liquid cannot adhere to the polishing pad sufficiently. In severe cases, the polishing liquid is rejected and the polishing speed becomes extremely slow, resulting in time-consuming polishing. Moreover, even if the polishing liquid adheres to the polishing pad, the amount of the polishing liquid adhered is not even, and the object to be polished cannot be uniformly polished. In addition, there are dry parts on the polishing pad. When a small amount of polishing liquid is attached, only the solution is removed by evaporation or the like, which results in the agglomeration of the abrasive particles. It also becomes a defect on the surface of the semiconductor wafer, which is a scratch (abrasion ) Causes. Conversely, if the wettability of the polishing pad to the polishing liquid is too good, the solution in the polishing liquid will be absorbed by the surface of the polishing pad during the grinding operation, causing the polishing pad to swell, which will cause the stability of the polishing speed to deteriorate. Conventional polishing pads are often worrying due to the instability of the polishing speed caused by excessive wettability, so most of the surfaces of the polishing pads are water-repellent. In terms of polishing characteristics, in order to improve the planarity of an object to be polished, the polishing pads have a high modulus of elasticity, but the wettability of the polishing pads has not been sufficiently discussed. In recent years, due to the above reasons, it has been noticed that the wettability of the polishing pad to the polishing liquid needs to be improved to a certain degree, and gradually improved. Japanese Patent Laid-Open Publication No. 2000-173958 proposes to hydrophilize the surface of the polishing pad with an oxidizing medicinal solution or a surfactant to improve the wettability of the surface of the polishing pad. In Japanese Patent Laid-Open Publication No. 2000-237951, it is proposed that a sand cloth made of a non-woven cloth or a cloth made by impregnating an elastic body with a non-woven cloth is subjected to a hydrophilizing treatment with a hydrophilic solution to improve the wettability of the surface of the cloth. Sex. 5 In the aforementioned Japanese Patent Laid-Open Publication Nos. 2000-173958 and 2000-237951, in order to make the surface of the polishing pads secretably lifted, they are all made hydrophilic by using a certain agent on the matrix polymer material used to form the polishing pads.化 处理。 Processing. Therefore, the preparation of polishing pads requires a hydrophilizing agent and a hydrophilizing process, which is difficult to reduce the cost. Another object of the present invention is to provide a polishing pad capable of optimizing the wettability of the polishing liquid without hydrophilizing the matrix polymer material used to form the polishing pad (polishing layer) with a medicament. A polishing layer and a manufacturing method thereof, and a polishing pad capable of uniformly polishing an object to be polished with less scratches and maintaining a polishing rate capable of achieving a high polishing rate requirement, and a manufacturing method thereof. The polishing pad used for the above-mentioned high-precision polishing is generally a polyurethane foam sheet having a void ratio of about 30% to 35%. However, although the polyurethane foam sheet has good local flattening ability, if the compression 20 ratio is as small as about 0.5% to 1.0%, the cushioning property is insufficient, and it is difficult to apply an average of the entire wafer. pressure. Therefore, a soft buffer layer is usually provided on the back of the polyurethane foam sheet to form a laminated polishing pad, which is then used for polishing processing. In such a conventional polishing pad, the impregnated resin is widely used as a buffer layer. VII. Description of the Invention The non-woven fabric is a continuous cavity, so the polishing liquid used will penetrate into the aforementioned buffer layer. As a result, the hardness of the buffer layer is reduced, the compression characteristics are changed, and the overall characteristics of the polishing pad are changed. However, the grinding characteristics such as uniformity and polishing rate change over a period of time, resulting in a decrease in the yield of the wafer. Techniques for preventing the above-mentioned polishing liquid from infiltrating the resin nonwoven fabric of the conventional polishing pad buffer layer include the technique of covering the side of the buffer layer with a polishing layer as disclosed in Japanese Patent No. 2842865, and Japanese Patent No. 3152188. Disclosed is a technique for arranging a waterproof material between abrasive layers. However, the technology described in Japanese Patent No. 2842865 covers the sides of the buffer layer, so it is necessary to make the polishing layer into a special shape, or it is necessary to form a recess in the polishing layer and then embed the buffer layer to form a buildup. This will greatly reduce the productivity of the polishing pad. In addition, the technology disclosed in Japanese Patent No. 3152188 is to provide a waterproof material layer between the polishing layers. Therefore, during polishing, the polishing surface approaches the waterproof material layer as the abrasive layer wears. The rigidity of the polishing layer and the waterproof material layer The difference becomes more significant and affects the grinding characteristics. In addition, if the polishing layer is used within a range where this influence is not formed, the life of the polishing pad is shortened. Another object of the present invention is to provide a reduction in the hardness of the buffer layer and a small change in the compression characteristics, so that the overall characteristics of the polishing pad are small, and polishing characteristics such as uniformity and polishing rate will not make the finished wafer product after a period of time. Rate reduction of polishing pads. In addition, a polishing pad which is stable, has a high polishing speed, and has a long life is provided. 1222390 发明 Description of the invention [Disclosure of the invention] The semiconductor wafer polishing pad system of the present invention is an independent bubble type resin foam, and the number of independent bubbles of the foregoing polishing layer is 200 / mm 5 2 or more 600 or less. The number of bubbles is the number of bubbles on the surface obtained by cutting the polishing layer from any position. In addition, another semiconductor wafer polishing pad of the present invention has a polishing layer composed of a resin foam, and the average cell diameter of the closed cells is 10 to 30 μm to 60 μm. The average bubble diameter is obtained by measuring the surface bubble diameter obtained by cutting the polishing layer from any position. In another aspect, the polishing layer of the semiconductor wafer polishing pad of the present invention is a closed-cell resin foam, and the number of closed-cell bubbles of the aforementioned polishing layer is 15 200 pieces / mm 2 to 600 pieces / deletion 2 or less, and The average bubble diameter is 30 μm to 60 μm. In the independent-cell type resin foam constituting the aforementioned polishing layer, a high polishing rate can be obtained in a range of from 200 cells / L 2 to 600 cells / L 2. When the number of air bubbles is less than 200 pieces per second, the number of recessed holes (20 points of air bubbles) for holding the polishing liquid is reduced, and the amount of polishing liquid between the semiconductor wafer and the polishing pad that can achieve effective results during polishing is reduced. As a result, the polishing rate is reduced. In addition, when the number of air bubbles exceeds 600 / leg 2, the diameter of the air bubbles of the polishing pad will be as small as 10 μm or less, and the grinding debris or liquid agglomerates in the air bubbles will be dense and cannot fully achieve the effect of retaining the liquid. 19 1222390 发明 Description of the invention The method for controlling the number of bubbles and the diameter of the bubbles of the present invention can be controlled by adding the particle diameter and the amount of the particles when adding hollow particles. In addition, during mechanical bubble formation, it can be controlled by controlling the number, shape, and time of the rotation of the stirring blade during stirring, or by changing the amount of the surfactant added as an auxiliary agent for bubble formation. When the average bubble diameter of the independent bubbles of the foregoing polishing layer is less than 30 μm, or when the average bubble diameter exceeds 60 μm, the polishing rate will be reduced. In addition, the so-called independent bubbles in the above-mentioned invention refer to those that are circular, elliptical, or bubbles with similar shapes, and are not formed by combining two or more bubbles. In the present invention, any polishing pad having independent air bubbles can be used. The material is not particularly limited, but a polyurethane resin foam is preferred. Polyurethane resin has flexibility in addition to the necessary hardness, so it can reduce the small scars, i.e., scratches, applied to the object to be ground. 15 The so-called closed-cell polyurethane resin foam does not need to be 100% composed entirely of closed cells, and continuous bubbles may be partially stored. Independent bubble rate can be more than 90%. The closed cell ratio can be calculated by the following method. The closed cell ratio is obtained by cutting a 20-section section of the obtained foamed abrasive layer with a microtome, and presenting a microscope image of the cross-section with an image processing device image analyzer V10 (manufactured by Toyo Textile Co., Ltd.) to calculate the total area per unit area. The number of bubbles and the number of independent bubbles are calculated by the following formulas. Free cell ratio (%) = (Number of free cells / Total number of cells) X 100 Another 'the polishing pad of the present invention has 20 1222390 12 made of resin foam, the polishing pad of the invention description, and The thermal dimensional change is less than 3%. By setting the thermal dimensional change rate of the polishing layer of the polishing pad to be less than 3%, it is possible to obtain a temperature increase caused by the frictional heat generated during the polishing process, which can also reduce the flattening characteristics less than the conventional polishing pad. . 5 In the polishing layer of the polishing pad, the resin foam or the resin layer is preferably a polyurethane resin foam. The polyurethane resin foam can easily constitute a polishing layer having a thermal dimensional change of 3% or less. And during the polishing operation, the abrasive particles in the polishing liquid can be maintained on the surface of the polishing pad, so that the required polishing speed can be obtained. Polyurethane 10 ester resin foam has fine bubbles. The average diameter of the bubbles (pore diameter) is in the range of 30 μm to 70 μm. Ideally, it is in the range of 30 μm to 50 μm, and more preferably in the range of 30 μm to 40 μm. good. The resin foam is particularly preferably a closed-cell polyurethane resin foam. If the foaming state is not good, even if the thermal dimensional change rate is within the ideal range, the polishing characteristics may be lowered. In another aspect, the polishing pad of the present invention has a polishing layer composed of a resin foam, and the surface of the polishing layer has a coefficient of kinetic friction in the range of 0-1 to 10. By setting the dynamic friction coefficient of the surface of the polishing layer to be in the range of 0-1 to 10, a high polishing rate can be maintained, and the resistance when the crystal 20 circle is removed from the polishing pad after polishing is small, and there is no release clamp Abrasive pads that cause holding errors that do not cause wafer breakage and low operating efficiency. If the kinetic friction coefficient of the surface of the polishing layer is less than 0.1, the polishing rate will decrease and the polishing efficiency will be low. If the dynamic friction coefficient on the surface of the polishing layer is greater than 10, the clamp will be released when the polishing pad is removed from the surface of the object after polishing. 21 1222390 玖, description of the invention is incorrect. The dynamic friction coefficient of the surface of the polishing layer is more preferably in the range of 0.2 to 0.9. The dynamic friction coefficient of the surface of the polishing layer is in the environment of temperature (23 ± 2) ° C and humidity (50 ± 6)% RH. It is brought into contact with high heat-resistant glass Pyrex (5 pyrex, manufactured by Corning Corporation) and the temperature is 10 : A value measured at a pressure of 8 kPa and a speed of 20 cm / min. During the measurement, those with grooves on the polished surface will be trimmed to remove the grooves, and the friction coefficient of the polished layer itself will be measured. In the polishing pad, the resin foam is preferably a polyurethane resin foam. 10 In the present invention, any polishing pad having a dynamic friction coefficient within the above range and having independent bubbles can be used. The material is not particularly limited, but the use of independent bubble polyurethane resin foam is particularly desirable. The contact area between the polishing layer and the object to be polished is reduced due to bubbles on the surface, and it is possible to easily produce a polishing pad having a dynamic friction coefficient within the scope of the present invention. 15 The method of controlling the dynamic friction coefficient can be carried out by changing the surface shape and adding additives. The method of changing the surface shape can be controlled by controlling the shape of the grooves on the surface of the polishing pad, or by changing the surface roughness of the surface of the polishing pad with a diamond dresser or the like. Furthermore, in the way of adding the additives, by changing the amount of the surfactant added or the content of the surfactant, the bubble formation state of the aforementioned polishing pad containing bubbles can be changed, and the dynamic friction coefficient can be changed. Another 'the polishing pad of the present invention is a polishing layer having a resin layer, and the aforementioned polishing layer was subjected to abrasion wheel abrasion test before and after a 24-hour crush test in a potassium hydroxide aqueous solution (40 ° C) of pH 12 · 5 ( Taber abrasion 22 1222390 (Invention test) The abrasion amount is less than 10mg. Generally, when a polishing pad is actually used, a polishing liquid of about pH 11 to 12 is usually dripped on the surface of the polishing pad. Therefore, by using the abrasion amount difference of less than 10 mg as the material of the abrasive layer through the aforementioned abrasion wheel abrasion test, a polishing pad having a small change in polishing characteristics over a period of time and a stable polishing speed can be obtained. The smaller the abrasion amount difference is, the more preferable it is, and it is more preferably 7 mg or less. The value of the aforementioned abrasion amount is in the range of about 30 mg to 80 mg, which is ideal from the viewpoint of ensuring basic polishing characteristics and polishing pad life. The details of the aforementioned abrasion amount can be measured by the method described in the examples. 10 In the aforementioned polishing pad, the resin foam or resin layer is stored at 40 ° C.

The elastic modulus should be above 270Mpa. If the aforementioned storage elastic modulus does not reach 270 MPa, sufficient flatness characteristics cannot be obtained. A polishing pad using a polyurethane composition with such a high elastic modulus is very useful for the planarization of device-based wafer polishing, and it is also useful for glass polishing where a highly elastic modulus polishing pad is required. In addition, such a polishing pad can perform polishing operations with stable and high polishing efficiency. The aforementioned storage elastic modulus is preferably 280Mpa or more, more preferably 300Mpa or more. The so-called storage elastic modulus in the present invention refers to the storage elastic modulus of the abrasive layer in a dynamic viscoelasticity measuring device using a test fixture for tensile testing, and applying a sine wave vibration and measuring at a frequency of 20 1Hz under an environment of 40 ° C. The measurement conditions of the storage elastic modulus can be referred to the conditions during grinding. That is, because the polishing pad is pressed against the object to be processed during grinding and both sides perform a rotational movement, and the movement is about 1 Hz, and the frictional heat at this time causes the polishing pad to reach about 40 ° C, so the measurement conditions of the storage elastic modulus Based on these conditions. However, regarding 23 1222390 发明, description of the invention The measurement of the tensile test 'After review by the inventors, it was found that the measured value of the compression test is approximately the same as the measured value of the tensile test, and a simpler tensile test is used for measurement. # In the aforementioned polishing pad, the resin foam or resin layer is preferably a polyurethane · 5 resin foam. Polyurethane resin has flexibility in addition to the necessary hardness, so it is a material with good abrasion resistance, and is most suitable as a material for polishing pads. In addition, polymers with desired physical properties can be produced by various changes in the composition of the raw materials. It is also a major feature of polyurethane resins and is suitable as a forming material for grinding concrete. In addition, the polyurethane microfoams have fine bubbles that are uniform and have higher hardness than those of the same density. The fine foam structure of the polyurethane microfoam can achieve a high elastic modulus, and can ensure the bubbles of the polishing liquid supplied when used as a polishing pad. The micro-foam structure is very effective in maintaining the abrasive particles in the polishing liquid in the pores of the micro-foamed part and stabilizing the milling speed by 15%. Therefore, the micro-bubbles can sufficiently increase the milling speed and achieve a stable effect. Polyurethane microfoam has a micro-gas ® bubble diameter (pore diameter) of 70 μm or less on average, preferably 50 μm or less, and more preferably 40 μm or less. Generally speaking, it is preferably within a range of 30 μm to 40 μm. The resin foam is preferably a closed-cell polyamine. 20 oxalate resin foam. In the aforementioned polishing pad, the density of the polyurethane resin foam is preferably within a range of 0.67 g / cm 3 to 0.90 g / cm 3. If the density of the polyurethane resin foam becomes smaller, it tends to be difficult to reach a sufficient storage elastic modulus. Therefore, the density of the polyurethane resin foam is 24 1222390 玖, and the degree of explanation of the invention is preferably 0.67g. / cm 3 or more, and more preferably 0.68 g / cm 3 or more. Conversely, if the density of the polyurethane resin foam becomes large, the number of fine bubbles on the surface of the polishing layer tends to be insufficient and it may not be ideal from the standpoint of the polishing rate. Therefore, the density of the polyurethane composition It is preferably below 0.90 g / cm 3 and more preferably below 0.88 g / 5 cm 3. In the aforementioned polishing pad, the hardness of the polishing layer is preferably 45 or more and less than 65 as measured by a D-type rubber hardness meter. The compression ratio of the polishing layer is preferably 0.5% or more and 5% or less. In the aforementioned polishing pad, the polyurethane resin foam preferably contains 10 0.05 wt% to 5 wt% of a polysiloxane surfactant. When manufacturing polyurethane resin foam, pre-mixing a polysiloxane surfactant in the polyurethane raw material is beneficial to the stable production of fine bubbles, and it does not damage the physical properties of the polyurethane. In the state, a polyurethane resin foam with uniform air bubbles is produced stably. 15 In the polishing pad of the independent bubble polyurethane resin foam, when the polysiloxane interface active dose is less than 0.05 λνί%, it will be difficult to obtain a stable independent bubble foam. However, when the dosage is more than 5wt%, the strength of the polishing pad is reduced due to the addition of the interface / tongue agent, and the planarization characteristics are deteriorated during polishing. 〇 In the present invention, the aforementioned polysiloxane surfactant is preferably a copolymer of polyalkylsiloxane and polyether. In the polishing pad of the present invention, the hardness of the polishing layer is preferably 45 or more and less than 65 as measured by a D-type rubber hardness meter. In addition, in the polishing pad of the present invention, the I shrinkage of the polishing layer is preferably 0.5% to 25 1222390 玖, and the description of the invention is 5% or less. The polishing pad just mentioned has a structure in which at least two layers of a buffer layer are laminated on the polishing layer in contact with the object to be polished, and the buffer layer is preferably softer than the polishing layer. The aforementioned buffer layer is preferably selected from polyester nonwoven fabric, polyurethane foam or polyethylene foam impregnated with urethane 5. Still another aspect of the present invention relates to a method for polishing a semiconductor wafer while rotating the polishing pad and contacting the semiconductor wafer while supplying a polishing agent between the polishing layer and the semiconductor wafer to perform polishing. With the aforementioned polishing method, the micro unevenness of the pattern produced by a device having a fine pattern formed on the semiconductor wafer or even the semiconductor 10 wafer can be planarized with a high polishing rate. In the aforementioned method for polishing a semiconductor wafer, the polishing layer is preferably a polyurethane resin foam containing 0.05 wt% to 5 wt% of a polysiloxane surfactant. 15 Yet another aspect of the present invention relates to a method for manufacturing a milled concrete, which includes a process for producing a polyurethane resin foam, that is, the first component containing a random acid compound or containing At least one of the second component of the active hydrogen-based compound is added to the total weight of the first component and the second component in an amount of 0.05wt% to 5wt ° / 0, and a polysiloxane surfactant containing no hydroxyl group is added. After the components of the surfactant and the non-reactive gas are mixed to prepare a bubble dispersion liquid in which the non-anisotropic gas is dispersed as fine bubbles, the remaining components are mixed in the bubble dispersion liquid and hardened. In addition, the present inventors have discovered that when using an isocyanate group-terminated prepolymer as the isocyanate group-containing compound of a foamed polyurethane raw material, 26 1222390 is used to control and control the content of the isocyanate group-terminated prepolymer in the invention description. The content of the isocyanate monomer is below a predetermined value, so that a polishing pad having good abrasion resistance and good polishing characteristics during polishing can be obtained, and then another invention is completed. That is, another method of the present invention is a method for manufacturing a foamed polyurethane s polishing pad. The method comprises adding an isocyanate-terminated prepolymer to an isocyanate-terminated surfactant and stirring in the presence of a non-reactive gas. Stirring procedure for forming a bubble dispersion, a mixing procedure of adding a chain extender to the bubble dispersion, and mixing to form a foaming reaction solution, and a hardening procedure of reacting and hardening the foaming reaction solution, and the aforementioned isocyanate The isocyanate 10 monomer content of the acid-vinegar terminal prepolymer is 20% by weight or less. The reason why the use of a prepolymer having an isocyanate monomer content of 20% by weight or less can improve the polishing characteristics is unknown, but it can be inferred that if the isocyanate monomer content exceeds 20%, the reaction between the chain extender and the isocyanate monomer will proceed first 'It is not enough to cause the high molecular weight of polyurethane to be caused by 10 of 15. The resulting foamed polyurethane is formed with fine bubbles without adding water-soluble resin particles or even hollow particles or polymers. For styrene foam beads and other materials used to form recesses on the polishing surface, the existence of the fine bubbles can keep the abrasive particles in the polishing liquid on the surface of the polishing pad during the polishing operation, so that a grinding speed of 20 in accordance with the requirements can be obtained. The diameter (pore diameter) of the micro-bubble bubbles of the foamed polyurethane is 70 μm or less on average, preferably 50 (im or less), and more preferably 40 μm or less. Generally, the range of 30 μm to 40 μm is In the above invention, the aforementioned isocyanate-terminated prepolymer is an aliphatic 27 1222390 玖, the description of the invention is at least one of the diisocyanate and the alicyclic diisocyanate (the isocyanate component) and the aromatic diisocyanate (the second isocyanate component). ) As an isocyanate component, and the ratio in the aforementioned isocyanate monomer is preferably the aforementioned first isocyanate component / second isocyanate component == 0.5 ~ 3.2 (weight ratio). 5 By using the aliphatic diisocyanate which reacts slowly, or even The cycloaliphatic diisocyanate S is used in combination with an aromatic diisocyanate as a diisocyanate component to constitute an isocyanate-terminated prepolymer. It can form a good grinding property and a suitable curing time when mixed with a chain extender. And easy to produce foamed polyurethane. 10 The aforementioned first isocyanate component is preferably 4,4, dicyclohexyl methyl Diisocyanate, and the aforementioned second isocyanate component is preferably toluene diisocyanate. By using such an isocyanate component, a resin for forming a foamed polyurethane can be prepared with good physical properties, especially grinding Foamed polyurethane with good characteristics. 15 In addition, the isocyanate monomer in the isocyanate-terminated prepolymer has a hardening time of less than 0.5 when the weight ratio of the first isocyanate component to the second isocyanate component is less than 0.5. Formed into a stable foamed polyurethane or even a mill. On the other hand, if the weight ratio of the first isocyanate component / the second isocyanate component exceeds 3.2, the hardness of the isocyanate-terminated prepolymer and the chain extender will be hardened. 20 The completion of the chemical process is time-consuming, resulting in increased cost and unsatisfactory effects. In the manufacturing method of the aforementioned foamed polyurethane polishing pad, the amount of the polysiloxane surfactant used in the aforementioned application process should account for the polymer concentration. In the amino acid vinegar, it is in the range of 0.05% to 5% by weight. 28 1222390 玖, description of the invention When the foamed polyurethane is produced, it is mixed with the polyurethane raw material in advance. The combination of polysiloxane surfactants will be beneficial to the stable production of fine air bubbles without damaging the physical properties of the polyurethane, and can stabilize the production of polyfoam foams with uniform bubbles. 5 When the amount of the surfactant added is less than 0.05% by weight, fine foams may not be obtained. Conversely, if the amount of the surfactant exceeds 5% by weight, the pores in the polyurethane foam may not be obtained. As the number of (bubbles) increases, it is difficult to obtain a polyurethane foam with high hardness. In addition, due to the effect of polysiloxane surfactants on plasticizing polyurethane, 10 will reduce the polishing pad. Strength and weaken the polishing characteristics. The method of manufacturing the polishing pad described above should include a lamination procedure of laminating the soft porous sheet on the polishing pad. By providing the soft porous sheet as a buffer layer, more flattening characteristics can be obtained Best polishing pad. 5 Yet another invention relates to a polishing pad formed by using polyurethane as a main constituent material composed of an organic polyisocyanate, a polyol, and a hardener. The main component of the hardener is 4, 4, -Methylene bis (o-chlorobenzylamine) 'and the number average molecular weight of the aforementioned polyol is in the range of 500 to 1600', and the molecular weight distribution (weight average molecular weight / number average 20 molecular weight) is not included. Polytetramethylene glycol up to 1.9. Also, another polishing pad of the present invention is a polishing layer containing a polymer material as a matrix material, and the swelling degree of the polymer material when immersed in a pH11 sodium hydroxide aqueous solution at 20 ° C for 24 hours is Within the range of 2% to 15%. 29 1222390 发明. Description of the invention In the present invention, the matrix material used to form the polishing layer of the polishing pad is a polymer material having a specific degree of swelling that swells when wet and softens its surface. The grinding 1 pad using a polymer material with a specific degree of swelling has a flatness better than those with hollow microspheres containing high-pressure gas dispersed in it. 5 In addition, in the grinding process, the water-based grinding fluid containing a solvent and abrasive particles is used. In the presence, the surface of the abrasive layer is softened by swelling and the surface hardness is reduced, so there is no problem of scratches. Due to the above effects, the above-mentioned grinding pad of the present invention can achieve the effects of improving the flatness and reducing the coexistence of scratches. φ Describes the degree of swelling of the two molecular materials. The polymer material used to form the matrix of the abrasive layer. The polymer material is a calibration process in the presence of an aqueous polishing solution. The estimated value σ specifically means 'system'. The polymer material was cut into a W-shaped sheet of a field, and immersed in a pH11 sodium hydroxide aqueous solution at 20 ° C for 24 hours, and then the value obtained according to the following formula. Swelling degree (%) = [{(weight after 24 hours) one (original weight)

15} / (original weight)] x100 The aforementioned swelling degree is in the range of 2% to 15%. If the degree of swelling becomes smaller, the softening of the abrasive layer during the grinding process is not complete, and the benefit of reducing scratches is small. Therefore, the aforementioned degree of swelling should be above 2%, and more preferably above 2.5% · Terabetsu is better than 3 / °. Conversely, if the degree of swelling becomes large, the abrasive layer may be excessively softened. Therefore, the aforementioned degree of swelling is preferably 15% or less, more preferably 10% or less, and particularly preferably 8% or less. In addition, the surface of the abrasive layer formed by the polymer material with the aforementioned swelling degree is preferably 52 (Slow and D hardness). In a general state, from the viewpoint of flatness, the range is about 75, and 55 ~ The range of 70 is more than 30 1,222,390, and the invention description is ideal. The reduction in hardness of the surface of the abrasive layer during the grinding process can be inferred from the degree of swelling, but the degree of the degree of swelling is the same as that described above (when immersed in a 20 ×: PHII sodium hydroxide aqueous solution for 24 hours). The hardness should be reduced by about 4 ~ 10, and more preferably by 5 ~ 8. 5 In the aforementioned polishing pad, the polymer material used as the matrix material of the polishing layer is polyurethane, and the polyol compound constituting the polyurethane is preferably a water-soluble polymer polyol. In order to improve the flatness of one of the polishing characteristics of the polishing pad (polishing layer), it is necessary to harden the entire polishing layer. This can be done by selecting a hard material, that is, a material with a high modulus of elasticity, as the polymer material used to form the abrasive layer. Among the polymer materials, the most important feature of polyurethane is that it can obtain the required physical properties through various changes to the composition of the raw materials, and it is easy to select a high elastic modulus material that is most suitable for polishing pads with improved flatness. In addition, a polyurethane-based material with excellent abrasion resistance is the most suitable material for the polishing layer. In addition, the aforementioned swelling degree of the polyurethane formed into a high-molecular material can be adjusted by using a hydrophilic compound as a constituent in the polyurethane, but it is desirable to use a high water-solubility The molecular polyol is adjusted as a polyol compound. In the aforementioned polishing pad, the polyurethane used as the matrix material of the polishing layer, 20 is preferably a foamed polyurethane having fine air bubbles. Polyurethane is a foamed polyurethane containing fine air bubbles, so that the abrasive particles in the polishing liquid can be sufficiently maintained on the surface of the polishing pad during the grinding operation, so that the required grinding speed can be obtained. Foamed polyurethane has uniform fine air bubbles and higher hardness than those of the same density. Such a foamed polyamine 31 1222390 玖, description of the invention The fine foaming structure of the formate can make the polyurethane highly elastic modulus while maintaining the polishing liquid supplied when used as a polishing pad to ensure polishing speed. The micro-foam structure is very effective for maintaining the abrasive particles in the polishing liquid in the pores of the micro-foaming part and stabilizing the polishing speed. Therefore, the fine 5 bubbles can sufficiently increase the polishing speed and achieve a stable effect. The fine bubbles having a foamed polyurethane are those having an average bubble diameter of 70 µm or less, preferably 50 µm or less, and more preferably 40 µm or less. Generally speaking, it should be in the range of 30 μm to 40 μm. In the foregoing polishing pad, the density of the foamed polyurethane 10 as the matrix material of the polishing layer is preferably in the range of 0.67 g / cm 3 to 0.90 g / on 3. When the polyurethane of the abrasive layer matrix material is used as the micro-foamed polyurethane, if the density becomes smaller, the flatness is insufficient. Therefore, the density of the micro-foamed polyurethane is preferably 0.67 g / cm 3 The above is more preferably 0.68 g / cm 3 or more. Conversely, if the density of the micro-foamed polyurethane is increased, the number of 15 micro-bubbles on the surface of the abrasive layer will be reduced, which is not ideal from the viewpoint of the polishing speed. Therefore, the density of the micro-foamed polyurethane is appropriate. It is 0.90 g / cm 3 or less, and more preferably 0.88 g / cm 3 or less. In the aforementioned polishing pad, the foamed polyurethane which becomes the matrix material of the polishing layer preferably contains a polysiloxane surfactant. 20 In the production of foamed polyurethane, pre-mixing a polysiloxane surfactant in the raw material of polyurethane is beneficial to the stable formation of fine air bubbles, and it is not suitable for polyurethane S Physical properties' and can stably produce fine and uniform foamed polyurethane. In the aforementioned polishing pad, the storage elastic modulus of the polishing layer at 40 ° C should be 32 1222390 玖, and the invention description is 270 MPa or more. The polishing layer is composed of the above-mentioned polymer material as a matrix material, and a sufficient flatness can be obtained by forming a high elastic modulus of 270 MPa or more by describing the elastic modulus of the polymer. The polishing pad using such a high-elasticity modulus polymer material 5 is very useful for planarization of device-based wafer polishing, and it is also useful for glass polishing applications that require a high-elasticity modulus polishing pad. In addition, the polishing pad can perform polishing operations with stable and high polishing efficiency. The aforementioned storage elastic modulus is preferably 280Mpa or more, more preferably 300Mpa or more. 10. The present invention relates to a method for manufacturing the aforementioned polishing pad, which includes a process for manufacturing a micro-foamed polyurethane, that is, the first component containing an isocyanate group-containing compound or the active hydrogen group-containing compound. At least one of the second component of the compound is added in an amount of 0.1% by weight to 5% by weight based on the total amount of the first component and the second component. A polysiloxane-based surfactant that does not contain a hydroxyl group, and then the components to which the aforementioned surfactant is added are stirred with a non-reactive gas to prepare a bubble dispersion solution in which the non-reactive gas is dispersed into fine bubbles. The remaining components are mixed and hardened in the bubble dispersion. In addition, another polishing pad of the present invention includes a polishing layer using a polymer material as a matrix material, which is characterized in that the contact angle of the polymer material with water is 20 to 70. ~ 95. Within range. In the present invention described above, a polymer material having a moderate wettability is used as a matrix material for forming a polishing layer of a polishing pad. Such a polishing pad having a polishing layer using a polymer material having a moderate wettability does not need to be subjected to a hydrophilization process in addition to the procedure for manufacturing the polishing layer of the polishing pad. Therefore, the manufacturing procedure is simple, and The polishing liquid has a good tight binding property, and can evenly grind the object to be polished, with few scratches, and can maintain a polishing speed that meets the requirements of a high polishing rate. Among them, the wettability of the polymer material is evaluated by using the polymer material itself. The contact angle is greatly affected by the state of the surface of the polymer material, so it is measured under the following conditions. The polymer material is formed into a film with a thickness of about 100 μm by a hot press. The temperature and pressure are appropriately set depending on the polymer material. For example, in the case of polyurethane, it is 2 and about 5 MPa. The contact angle meter ca-x (produced by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of the obtained film with water by the silk droplet method. Generally, the surface of the polishing pad is not flat when viewed microscopically. For example, in order to improve the retention of the abrasive particles in the polishing liquid, the polymer material is foamed, or the channel processing is performed to uniformly disperse the polishing liquid and discharge the abrasive debris, or to further improve the retention of the abrasive particles. The contact angle for trimming to improve the grinding speed also depends on the surface shape under this special microcosm. That is, the value of the contact angle varies depending on the shape of the surface, and sometimes it cannot be measured from the shape. Therefore, the contact angle was measured on a flat film surface as described above. The aforementioned contact angle is at 70. Within the range of ~ 95 °. Less than 70. When the obtained polishing pad is affected by the surface shape, the wettability of the polishing liquid is too large, and the solution in the polishing liquid is absorbed inside the polishing pad, causing the polishing pad to swell, and the stability of the polishing speed is deteriorated. Contact angle super fruit 95. At this time, the obtained polishing pad is affected by the surface shape, the polishing liquid cannot be completely adhered to the polishing pad, and the polishing speed becomes small. Also, 1222390 玖, description of the invention Even if the polishing liquid adheres to the polishing pad, the polishing object cannot be uniformly polished due to the uneven amount of the polishing liquid. Further, a dry portion is formed on the polishing pad, and when a small amount of polishing liquid is adhered there, only the solution is removed by evaporation or the like 'and the abrasive particles are aggregated, which causes the formation of scratches. 5 The aforementioned contact angle should be 75. ~ 93. Range, and at 79. ~ 91. The range is more ideal. In the aforementioned polishing pad, the polymer material used as the matrix material of the polishing layer is polyurethane, and the polyol component of the polyurethane constituent is mainly an ether-based polyol, and a part of the ether-based polyol is preferably Ether-based water-soluble ethyl 10 «η 5 ^. 〇 In terms of the characteristics of the polishing layer of the polishing pad, in order to improve the flatness, it is better to use a harder (high elastic modulus), and to reduce scratches, use a softer (Low elastic modulus) is preferred. In short, in order to improve flatness and reduce scratches simultaneously, an abrasive layer with the most appropriate hardness is required. Among polymer materials, the biggest feature of polyurethane is that the required physical properties can be obtained by various changes in the composition of the raw materials. It is easier to select the material with the most appropriate hardness. In addition, polyurethane is a material with good abrasion resistance, especially resistance to abrasive fluids, and is most suitable as a material for abrasive layers. The general polyurethane has low wettability and a large contact angle with water of 20%. In particular, the ether-based polyurethane has less wettability than the polyester-based polyurethane. However, the 'polyester-based polyurethane' is hydrolyzed by the aqueous solution in the polishing solution (mostly the test water), and the polymer properties are lowered and the polishing characteristics are lowered. Therefore, the polyurethane used as the polymer material of the polishing layer is preferably a polyether-based polyurethane. By including polyurethane-based 35 1222390 构成 in polyurethane constituents, and water-soluble ethylene glycol described in the invention, the wettability of polyether polyurethane to water can be adjusted to the optimum contact angle. 70. ~ 95. Within range. In the aforementioned polishing pad, the polyurethane used as the base material of the polishing layer is preferably a foamed polyurethane having fine bubbles. 5 Because polyurethane is a foamed polyurethane with fine bubbles, it not only achieves the best wettability of the polishing liquid, but also can maintain the polishing in the polishing liquid on the surface of the polishing pad during the polishing operation. Grain, so it can get the required grinding speed. The fine bubbles of the foamed polyurethane should have an average diameter (pore diameter) of 70 μm or less, ideally 50 μm or less, and more preferably 40 Km or less. Generally speaking, it should be in the range of 30 μm to 40 μm. In the aforementioned polishing pad, the foamed polyurethane as the matrix material of the polishing layer preferably contains a polysiloxane surfactant. The invention also relates to a method for manufacturing a polishing pad having a polishing layer 15 composed of a foamed polyurethane containing fine bubbles; the contact angle of the foamed polyurethane is described. Tied to 70. ~ 95. Within this range, the manufacturing method of the polishing pad includes the following procedures, namely: (1) Stirring procedure, which is based on the addition of a polysiloxane surfactant to an isocyanate-terminated prepolymer and stirring in the presence of a non-reactive gas Bubbles are divided into 20 liquid dispersions; (2) A mixing procedure is to add a chain extender to the aforementioned bubble dispersion to mix to form a foaming reaction solution; (3) A hardening procedure is to cause the aforementioned foaming reaction solution to harden by reaction. The manufacturing method of the aforementioned polishing pad preferably includes a lamination process of laminating the flexible porous sheet on the aforementioned polishing layer. In addition, another polishing pad of the present invention includes at least a polishing layer and a buffer layer, and the swelling ratio of the buffer layer to water is 40% or less. By setting the buffer layer of the polishing pad to a water swelling ratio of 40% or less, the reduction in hardness and the change in compression characteristics are small, so a polishing pad can be produced with small changes in overall characteristics and no uniform A polishing pad in which the polishing characteristics such as the sentence and the polishing rate are changed over a period of time, which reduces the pass rate of the wafer. In addition, a polishing pad having a stable high polishing speed and a long life can be obtained. The swelling ratio is calculated by immersing the material used as the buffer layer in distilled water at a predetermined time and 10 predetermined temperature, and calculating the weight based on the following formula before and after the immersion. Moisturizing ratio (%) == [(weight after immersion-weight before immersion) / weight before immersion] X 100 'J said the buffer layer can also be an independent bubble type resin foam , Or may be 15 non-foaming resin. The monthly polishing wafer is preferably used for polishing semiconductor wafers or glass substrates for precision machines. Brief Description of the Drawings Fig. 1 is a schematic view showing a semiconductor polishing apparatus. Fig. 2 is a schematic diagram showing the structure of a polishing pad. 3f, a), (The figure is a schematic diagram showing a method for measuring a dynamic friction coefficient. [Poor application mode] ^ A preferred embodiment of the invention 37 玖, description of the invention < [I] polishing pad > polishing of the present invention In the pad, there is no particular limitation on the material for forming the polishing layer. For example, polyurethane, polyester, polyamide, acrylate resin, etc. can be used. Among them, based on the aforementioned good abrasion resistance, Polyurethane can be used for various reasons such as various changes in the composition of the raw materials and can easily constitute a polishing layer. Polyurethane resin is described below as the material for forming the polishing layer. Polyurethane resin It is composed of polyisocyanate, polyol compound and chain extender, especially the foamed polymer obtained by reacting and curing the isocyanate-terminated urethane prepolymer and the organic diamine compound as a chain extender in a foamed state. The isocyanate-terminated ethyl amine acetate prepolymer is obtained by reacting a polyhydric alcohol compound known in the technical field of polyisocyanate and polyurethane with an excess of isocyanate groups. The polyisocyanate may be a compound known in the field of polyurethane without particular limitation. The polyisocyanate can be exemplified by the following types, such as: 2,4-diisocyanate toluene, 2,6-diisocyanate Toluene, 2,2, -diisocyanate dibenzine, 2,4'_diisocyanate diphenylmethane, 4,4, _diisocyanate diphenylmethane, 1,5-naphthalene diisocyanate , Aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, ethyl diisocyanate, 2,2,4 -Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4 · cyclohexane diisocyanate, 4,4, -dicyclohexylmethane diiso Alicyclic 1222390 醋 such as cyanate vinegar, isophorone diisocyanate, norformyl diisocyanate, family diisocyanates, etc. These can be used singly or in combination of two or more. Polyisocyanate removal In addition to the above-mentioned diisocyanate compounds, polyfunctional polyisocyanate compounds having three or more functions can also be used. A series of isoisolactate additions such as Desmodur-N (Desmodur-N, manufactured by Bayer) or Durande (Duranate, manufactured by Asahi Kasei Corporation) are commercially available. Among the aforementioned diisocyanates, 4,4, -dicyclohexylmethane diisocyanate (hydrogenated MDI = HMDI) and diisocyanate xylbenzene are preferably used in combination as described above. The ideal state of the foamed polyurethane is 2,4-diisocyanatobenzene / 2,6-diisocyanate toluene = 100/0 ~ 60/40 (Molar ratio). The polyol compound may be a polyol known in the technical field of polyurethane 15 acid esters such as hydroxyl-terminated polyester, polycarbonate, polyester carbonate, polyether, polyether carbonate, polyester ammonium, etc. However, among them, polyether and polycarbonate having good hydrolysis resistance are preferable, and polyether is particularly preferable from the viewpoint of price and melting viscosity. When taking into consideration the alkali resistance of the polyurethane resin, it is preferable to use an ether polyol or polycarbonate polyol Sf * as the multi-age compound. 20 In addition, the number-average molecular weight of these polyols is not particularly limited, but from the viewpoint of the elastic properties of the polyurethane foam to be produced, it is preferably in the range of 500 to 5000, and in the range of 500 to The range of 3000 is more ideal. If the number average molecular weight of the polyhydric alcohol is less than 500, the poly 39 1222390 produced by this method is described. The invention shows that the urethane foam does not have sufficient elastic properties and is easy to form brittle. Polymer, and the polishing pad using the polyurethane foam as a matrix is too hard, which causes scratches on the polished surface of the object to be polished. Since it is easy to wear, it is also not ideal from the viewpoint of the life of the polishing pad. 5 Conversely, if the number average molecular weight exceeds 5000, the polishing pad based on the polyurethane foam obtained will become soft, and satisfactory flatness cannot be obtained. Polyether polyols can include at least at least one starting compound having a reactive hydrogen atom and epoxy resins such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, propylene oxide, etc. Take one reaction product as an example. Examples of the starting compound having a reactive hydrogen atom include water, bisphenol A, and glycols used in the production of polyester polyols described below. The polyether polyol may be exemplified by polytetramethylene glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (peg), and the like. For materials with good resistance, polytetramethylene glycol is particularly preferred. Polycarbonate polyols having a base may be exemplified by 1,3-propanediol, 1,4-butanediol, ι-6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, and / or poly (ethylene glycol). The reaction of diols such as tetramethyl glycol with dicarbonyl carbonyl, diallyl carbonate (such as diphenyl carbonate) or cyclic carbonate (such as propylene carbonate) to produce 20 products is taken as an example. Examples of the polyether polyol include polybutylene adipate, polyhexamethylene adipate, and polycaprolactone polyol. Also, the aforementioned polyester polyol is exemplified by a reaction product of a diol and a carboxylic acid dibasic salt. However, in order to improve the hydrolysis resistance, the longer distance between the ester bonds is 40 1222390 玖. A combination of long chain components is particularly desirable. ^^ Yiu Biya is specially limited, but the following can be taken as examples, such as: ethylene glycol, 1,3- and propylene glycol, M_ & 2,3 · butanediol, M-hexanediol, octane Alcohol, neopentyl glycol, cyclohexanedimethanol, 1,4-bis- (methyl) -cyclohexane, 2-methyldecapropanediol, 3-methyl-1,5-pentanediol, 2 , 2,4-trimethyl-u-pentanediol, diethylene glycol, propylene glycol, triethylene glycol, propylene glycol, propylene glycol and the like. 10

As the diacid salt of the polyacetate polyol, an aliphatic, cycloaliphatic, aromatic, and / or heterocyclic carboxylic acid dibasic salt can be used without particular limitation, but it is necessary to prepolymerize the resulting terminal NCO The material is made into liquid or low melting viscosity, so it is suitable to use aliphatic or alicyclic carboxylic acid dibasic salt. When using aromatics, it is better to use aliphatic or alicyclic slow acid at the same time.

The suitable carboxylic acid dibasic salts mentioned above can be exemplified by the following, for example: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, 15 tetraphthalic acid, naphthalene Dicarboxylic acid, o-cyclohexanedicarboxylic acid, m-cyclohexanedicarboxylic acid, p-cyclohexanedicarboxylic acid, dimer fatty acid, oleic acid and the like. The polyester polyols described above can also be used as ring-opening polymers such as ε-caprolactone or polyesters of polycondensates of hydroxycarboxylic acids such as ε-hydroxycaproic acid. The polyester polycarbonate polyol may be, for example, a reaction product of a poly 20-ester diol such as polycaprolactone polyol and an alkylene carbonate, reacting ethylene carbonate with a polyol, and then reacting the obtained reaction mixture with an organic compound. A reaction product obtained by the reaction of a dicarboxylic acid, etc., as a material having excellent alkali resistance. In the isocyanate-terminated urethane prepolymer, in addition to polyol compounds, low-molecular-weight polyols are also used. Examples of the low-molecular-weight polyhydric alcohols include the glycols used in the above-mentioned production of poly 41 1222390 玖, the description of the ester polyols, and diethylene glycol, L3 · butanediol, and 3-methyl-1,5-pentane are suitable. Any one of diol and 1,6-hexanediol or a mixture thereof. If a diol having a chain length longer than 1,6-hexanediol is used, a polishing layer with a moderate hardness of the reactivity at the time of casting molding or the final polyurethane molding material can be obtained. When producing a foamed polyurethane having fine bubbles for forming a polishing layer, the above-mentioned polyols may be used alone or in combination of two or more kinds. If necessary, tri- or more functional components can be used together. Φ The above-mentioned polyhydric alcohol compounds and low-molecular-weight polyols mainly use bifunctional 10 components, but the simultaneous use of trifunctional or higher functional components can keep the thermal dimensional change rate of the obtained polishing pad stable below 3%, which is also ideal. Implementation form. The isocyanate component is appropriately selected depending on the pot life required during casting and molding, and it is necessary to form the resulting terminal NC〇 prepolymer to have a low melting viscosity of 15, so it is used alone or two or more kinds are used. mixture. As the organic monoamine compound used as the chain extender of the isocyanate-terminated prepolymer in the present invention, a known chain extender can be used without particular limitation. The chain extender is an organic compound having at least two active hydrogen groups, and the active hydrogen group can be exemplified by a hydroxyl group, a primary or secondary amine group, and a mercapto group (SH). ♦ 20 is an example. Specifically, for example, 4,4, · methylenebis (o-aniline) (MOCA), 2,6-digas-p-phenylenediamine, 4,4, _methylenebis (2,3 _Dichloroaniline), 3,5_bis (methylthio) -2,4_toluenediamine, 3,5_bis (methylthio)-2.6-toluenediamine, 3,5_diethyltoluene _2,4_diamine, 3,5_diethyltoluene_ 2.6-diamine, propylene glycol-di-p-aminobenzoate, -bis (fluorenylphenylsulfide 42)

• V • V 1222390 玖, invention explanation group) Ethyl alcohol, 4,4'-diamine-3,3'-diethyl-5,5'-dimethylbenzyl alcohol, or, The above-mentioned low-molecular-weight polyol is taken as an example. These may be used singly or in combination of two or more. The ratio of the polyisocyanate, the polyol compound, and the chain extender can be variously changed according to the molecular weight of each compound or the required physical properties of the polishing pad. In order to obtain a polishing pad having the required polishing characteristics, the number of isocyanate groups of the polyisocyanate relative to the total number of active hydrogen groups (hydroxyl + amine groups) of the polyol compound and the chain extender should be in the range of 0.95 to 1.15, and It is more preferable to be in the range of 0.99 to 1.1. 10 The ratio of the polyol compound to the low-molecular-weight polyol can be appropriately set depending on the characteristics required of the polyurethane resin produced by them. Among them, for example, the grinding mill in item 23 of the scope of patent application, from the viewpoints of hydrolysis resistance, elasticity, abrasion resistance, etc., the polyhydric alcohol needs to contain polytetramethylene glycol. In addition, the polytetramethylene glycol must meet the conditions that the number average molecular weight is in the range of 500 to 15 1600, and the molecular weight distribution (weight average molecular weight / number average molecular weight) is less than 1.9. · The number average molecular weight is a value obtained from a hydroxyl value measured in accordance with JIS κ 1557. The molecular weight distribution is a value measured under the following conditions. GPC device IX—ι〇Α (Shimadzu Corporation) 20 • Sample preparation: Dissolve approximately 4 mg of the sample in 2 ml of tetrahydrofuran • Chromatography tube • 2 MIX-E (manufactured by PL Corporation) • Layer Analytical tube temperature: 40 ° C • Mobile phase: Tetrahydrofuran • Flow rate: 0.7ml / min 43 1222390 玖, invention description • Injection volume: 60μ1 • Detector: RI (37 ° C) • Molecular weight distribution: standard PPG ( Polypropylene polyol) If the number average molecular weight of the tetramethylene glycol is less than 500, then the polycarbamidine produced at 5 does not have sufficient elasticity and forms a brittle polymer. In addition, the polishing pad made of the polyurethane is too hard, which causes a scratch on the polishing surface of the object to be polished, and the effect is not ideal. In addition, since it is easy to wear, it is not satisfactory from the viewpoint of the life of the polishing pad. 10 If the number-average molecular weight exceeds 1600, the polishing pad made of the polyurethane thus obtained becomes soft, and satisfactory flattening processing cannot be completed, and the effect is not satisfactory. Also, if the molecular weight distribution of polytetramethylene glycol is 1.9 or more, the temperature dependence of the hardness (elastic modulus) of the polyurethane obtained therefrom will be increased by 15 'and the polyurethane In the finished polishing pad, the difference in hardness (elastic modulus) due to temperature becomes larger. As described above, the frictional heat generated between the polishing pad and the workpiece causes the temperature of the polishing pad to change during polishing. Therefore, a difference in the polishing characteristics results in an unsatisfactory effect. In addition to polytetramethylene glycol, the aforementioned polyols can be used in combination as long as the aforementioned polyol compounds and low-molecular-weight polyols do not impair the characteristics of the polishing pad 20. In addition, if the polishing pad of item 23 of the patent application scope, from the viewpoint of the mechanical properties and abrasion resistance characteristics of the polyurethane produced and the polishing pad manufactured by it, the hardener needs to be 4,4, _ Methylene bis (o-aniline) is the main component 44 1222390 玖, and is constructed according to the description of the invention. However, as long as the characteristics of the polishing pad are not impaired, in addition to 4,4, methylene bis (o-chloroaniline), the hardener can also be used in combination with 2,6-dichloro-p-phenylenediamine, 4 ,, Polyamines such as 4, -methylenebis (2,3-digas aniline), or the aforementioned low-molecular-weight polyols. 5 In addition, the form of the polishing pad in the scope of the patent application No. 23 can also be composed of a polyurethane matrix impregnated with a polymer microelement containing a pressurized gas, as seen in Japanese Patent No. 3013105. As seen in Japanese Patent Laid-Open Publication No. 11-322878, it is composed of micro · foamed polyurethane dispersed with polystyrene beads. It can also be composed of fine-bubble polyurethane foam as seen in Japanese Patent Laid-Open No. 2000-10 P8374. The polyurethane resin of the present invention can be produced by applying a known urethane esterification technique such as a melting method and a solution method, but it is preferably produced by a melting method in consideration of cost, operating environment, and the like. The production of polyurethane can be carried out by any method such as a prepolymer method or a one-shot foaming method (One_15 shot process), but the prepolymer method is a method in which an isocyanate terminal prepolymer is synthesized from a polyisocyanate and a polyol compound in advance. It is suitable because it has good physical properties, and the chain extension and elongation agent reacts therewith. In addition, there are commercially available 20 isocyanate-terminated prepolymers made of polyisocyanate and polyol compounds. Those who are suitable for the present invention can use them and use the prepolymer method to make the polyurethane used in the present invention. polymerization. The isocyanate-terminated prepolymer is one having a molecular weight of about 800 to 5,000, and is excellent in processability and physical properties, and is therefore suitable for use. In addition, isocyanate-terminated prepolymers can also be used in combination of two or more types. Special 45 1222390 玖, description of the invention, especially for the production of foamed polymer with aliphatic or even cycloaliphatic diisocyanate and aromatic diisocyanate. In the case of amino acid, the ideal form is to mix the prepolymer with aliphatic or alicyclic diisotate and the prepolymer with fluorinated aromatic diisocyanate. Λ 5 A method for adjusting the residual ratio of isocyanate monomers. For example, a prepolymer with a small residual isocyanate monomer ratio can be produced, and an isocyanate monomer can be added to the prepolymer. The isocyanate monomer is removed from the prepolymer having a large residual ratio of isocyanate monomers by methods such as distillation and reduced pressure. The above-mentioned production of amidate is performed by mixing a first component containing an isocyanate group-containing compound and a second component containing an active hydrogen group-containing compound, and then hardening it. In the prepolymer method, an isocyanate-terminated prepolymer forms an isocyanate group-containing compound, and a chain extender forms an active hydrogen group-containing compound. In the one-step foaming method, the polyisocyanate forms an isocyanate group-containing compound, and the chain extender and the polyol compound form an active hydrogen group-containing compound. 15 The manufacturing method of the above-mentioned polyurethane resin may include, for example, a method of adding hollow beads, a method of forming a foam by a mechanical foaming method, and the like, but it is not limited thereto. It is also possible to use both of them simultaneously, but a mechanical foaming method using a polysiloxane surfactant having an active hydrogen group and a copolymer of polyalkylsiloxane and polyether is preferred. 20 In the production of polyurethane, it can be used before mixing and stirring the aforementioned polyurethane raw materials (containing the first component containing isonic acid ester group compounds and the second component containing active hydrogen group compounds), Or when mixing and stirring, the non-reactive gas is taken into the polyurethane raw material to absorb the bubbles, and then it is hardened and foamed to form a foamed state (ideally, hair with fine bubbles 46 1222390 玖, DESCRIPTION OF THE INVENTION A method for forming a polyurethane resin foam into a block. At this time, it is advisable to add a polysiloxane-based surfactant before the polyurethane raw material (containing the first component containing isocyanate compounds and / or the 28% containing active hydrogen-containing compounds), The components to which the aforementioned poly-stone oxygen-based 5-surface active agent is added are stirred with a non-reactive gas to disperse into fine bubbles, or when dispersed, the remaining components are mixed therein. Mixing a polysiloxane surfactant in advance with a polyurethane raw material is a very effective method for stably making fine bubbles. The polysiloxane surfactant used in the present invention is preferably a surfactant of a copolymer of polyalkyl 10 oxoxane and polyether. Specifically, the compounds represented by the following Chemical Formulae 1 to 6 can be exemplified. (Chemical 1) CCH, CH, X i I 3 s i 〇 (S Ι Ό) m (S i Ο) „S i (CHa) r I i CH, CH, (Chemical 2)

CHa CUz 11 x-s i 〇 (S i O) m I I CHa CHa

CHi IS i —X CHa (chemical 3) CH3 I (CH3) 3 si Q (si 〇) l " cm '"': CHa Si —X CH3 (chemical 4) CH, CHa I 1 x—S i CD (si 〇) BU 丨 CH3 CHa X CKz

(S i 〇) Λ S i -X CHa ch3 47 1222390 发明, description of the invention (Chem. 5)

CH3 CuHn C3 H5 0 (EG) a (PO) b H!!! (CH3) 5 S i 0 (S i 0) I (S i 0), (S i 0), S i (CH.) 3 i 1! CH2 CHS CH5 (Chemical 6) ch3

Rf i

C3 H5 Ο (EO) a H (CH3) a S i 0 (S i 0) i (S i 0) m (S i 0) n S i (CH3) 3 CH3 (Rf Cy Fzy + i) ch3 ch3 Chemical formula As the substituent X in Formula 1 to Chemical Formula 4, the following substituents can be exemplified. (Chemical 7)

~ Ca Η (Chemical 8) 〇

II ~ " C: Hs 0 (Cj Hi 0) * * -P ™ 〇Na i

OH (Chemical 9) ···· C;! H 6 〇 1 C 2 H: i O) 〇 C u H 5 〇) is R (Chemical 1 0)

-~ C ,, Hs O (CH; > CH (OH) CH2 O) a H (chemical: 1 1) ~ C, Hs (CH,) 2 CH, COO- (chemical 1 2) -C: 1 Hs O (C ;; H, O). SO, Na (Chem. 1 3) —Hs Ν '(CH5) 3 * C 1 " 48 Kan, Description of the Invention Among the substituents exemplified above, non-radical substituents Better. Examples of the poly bond include polyethylene oxide, polypropylene oxide, and copolymers thereof. These surfactants are examples, and are not particularly limited thereto. Polysiloxane-based surfactants include commercially available products such as SH_192, SH_193 (Toray Dow Cc, rning), L 5 Dove (Nippon Unicar, Japan), etc. As an example. In the present invention, the hardness of the polishing layer of the polishing pad in the state containing a surfactant should preferably be measured by a D-type rubber hardness tester to be 45 or more and less than 65qD. When the hardness is less than 45, the flattening characteristics will be deteriorated, and when the hardness is more than 65, the flatness will be flattened. The characteristics are good, but the polishing uniformity of the semiconductor wafer will deteriorate. The hardness of the rubbing buffer layer in the state of the present invention containing a surfactant is preferably measured by a D-type hardness tester "! And not more than 4 (). If it is 2 or more and less than 35, it is more desirable, and the particularly desirable is 5 or more and less than 30. If it is less than 1, the in-plane uniformity will deteriorate, and if it is more than 40, the planarization characteristics will deteriorate. In the present invention, the compression ratio of the polishing layer of the polishing pad is 0.5% or more. 5% or less. Because the compression ratio is within this range, a polishing pad with excellent uniformity can be obtained. The compression ratio can be expressed in the following formula. Compression ratio (%) = (T1 — T2) / TlxlOO where T1 is the expression The thickness of the layer from the unloaded state to a load of 3h (300g / cm2) and maintained for 60 seconds, and τ2 means the thickness of the layer from the state of T1 to a load of i80kPa and maintained for 60 seconds.说明 Description of the invention The polyurethane foam used as the polishing layer on the polishing pad in the present invention is cut with independent bubbles, and its density is above 订. If the density is less than 0.6 ', its strength will be significantly reduced and it will not be able to withstand grinding. Friction. Again, density

1 1 niL will open into a state of no bubbles, and the polishing rate will decrease when the polishing pad is formed. In the present invention, in order to improve the polishing uniformity of the object to be polished, the polishing pad can form a structure of at least two layers—a polishing layer for contacting the polishing object, and one for supporting the polishing layer and comparing with that. Abrasive layer is a soft buffer layer. At this time, as the buffer layer, a fiber non-woven fabric layer such as polyester non-woven fabric, nylon non-woven fabric, acrylic non-woven fabric can be used, or even such non-woven fabric is impregnated with urethane resin material, urethane resin, polyethylene resin, etc. Independent bubble foam. Among them, in terms of easy manufacture and low price, physical stability, etc., it is better to use polyester non-woven cloth, polyurethane foam or polyethylene foam impregnated with ethyl urethane. Urethane closed-cell foams are particularly preferred. By using this foam, it is possible to provide a polishing pad which is excellent in repeated load durability and inexpensive. The polishing pad may have an adhesive layer (tape layer) in addition to the polishing layer and the buffer layer. In the polishing pad of the present invention, the thickness of the polishing layer is preferably within the range of 0.8 brain to 2 coffee. In addition, the thickness of the buffer layer is not particularly limited, and can be appropriately set according to the material used, but is within 0.5 mm ~ In the range of 2 mm, the balance with the rigidity of the abrasive layer is ideal. The polishing pad manufacturing method of the present invention will be described using an isocyanate-terminated prepolymer as an example of the isocyanate group-containing compound. The manufacturing method of the polishing pad of the present invention includes the following procedures, namely: 1222390 玖, description of the invention (1) Stirring procedure for preparing a bubble dispersion liquid of an isocyanate-terminated prepolymer Add polysiloxane interface activity to the isocyanate-terminated prepolymer Agent, and stir with the non-reactive gas to disperse the non-reactive gas into fine bubbles to form a bubble dispersion. When the prepolymer is solid at normal temperature, it should be preheated to a suitable temperature and used after melting. (2) Mixing procedure of hardener (chain extender) Add the chain extender to the above-mentioned bubble dispersion, and mix and stir to form a foaming reaction solution. When the chain extender is a solid compound at normal temperature, it should be added after melting. 10 (3) Hardening procedure An isocyanate-terminated prepolymer mixed with a chain extender is poured into a predetermined mold and heat-hardened. The polyurethane resin foam produced by the above procedure is cut into a predetermined size and used as a polishing layer. 15 Non-reactive gas used in the production of polyurethane resin foam ′ is a gas composed of a normal temperature gas that does not react with isocyanate groups or active hydrogen groups. The gas can be sent into the liquid in a positive way, or the gas can be naturally mixed in while stirring. The non-reactive gas used to form fine bubbles is preferably non-flammable, and specific examples include rare gases such as nitrogen, oxygen, carbon dioxide, 20 helium or argon, or a mixed gas thereof, and The air that has been dried to remove moisture is most cost effective. In the present invention, stabilizers such as antioxidants, lubricants, pigments, fillers, antistatic agents, and other additives may be added to the polyurethane composition as necessary. 51 发明 Description of the invention The manufacturing process is also provided with a lamination process, which is attached to the sheet-shaped polishing layer 'before cutting to the size of the polishing pad or after cutting, if necessary, a flexible porous sheet is pasted to form a buffer layer, which is made 2-layer structured polishing pad. A stirring device for dispersing non-reactive gas into fine bubbles and dispersing it in an isocyanate-terminated prepolymer containing a polysiloxane surfactant. Any known stirring device can be used without special consideration. There are homogenizers, dissolvers, and biaxial planetary mixers. The shape of the If blades of the stirring device is not particularly limited, but fine bubbles can be obtained by using the beat-type falling blades, and the effect is ideal. In addition, in the stirring process, the bubble dispersion liquid is stirred, and the chain extension agent is added in the mixing process for mixing. It is also an ideal form to use different mixing devices. In particular, the stirring in the mixing procedure may not be a stirring for forming air bubbles, and a stirring device that does not involve large bubbles should be used. This type of agitator is most suitable with a planetary agitator. The stirring device of the stirring program and the mixing program can also use the same stirring device, and adjustment of the mixing conditions such as the rotation speed of the stirring blade should be adjusted as necessary before use. In the method for producing a polyurethane foam of the present invention, heating and secondary hardening are performed on the foam formed before the bubble dispersion liquid flows into the mold and reacts to a state where it cannot flow, thereby improving the foam. The effect of physical properties is extremely desirable. It is also possible to create a condition for the bubble dispersion to flow into the mold and immediately put it into the heating furnace for secondary hardening. Under such conditions, heat cannot be immediately transmitted to the reaction components, so the bubble diameter does not increase. The hardening reaction is performed under normal pressure, and the shape of the bubble is stable, and the effect is very satisfactory. Next, the obtained polyurethane resin foam was cut into 1222390 玖, and the description of the invention is suitable for the thickness of the polishing pad (polishing layer). The thickness of the abrasive layer is about 0 · 8 mm to 2 legs. Usually, a thin film with a thickness of about 1 · 2 legs is used. In addition, in addition to this method, a polyurethane component can also be poured into a mold having a cavity having a thickness equal to that of the polishing layer of the present invention. 5 In the present invention, known catalysts for promoting polyurethane reactions such as tertiary amines and organotin systems can also be used. The type and addition of the catalyst need to be selected in consideration of the flow time of the mold flowing into a predetermined shape after the mixing process. The manufacturing of the independent bubble polyurethane foam 10 used to form the grinding layer of the present invention can be used in a batch processing method of measuring the ingredients and mixing them in a container, and can also be used continuously in a stirring device. A continuous production method in which each component is supplied with a non-reactive gas, stirred, and a bubble dispersion liquid is sent out to produce a molded article. A groove can be engraved on the surface of the polishing layer, and a soft porous sheet 15 can be stuck on the inside to form a polishing pad. The grooves on the surface of the polishing layer have the function of discharging the grinding chips or materials from the contact surface between the object to be polished and the polishing pad. The shape of the grooves is not particularly limited, such as a rectangular, triangular, U-shaped, semi-circular cross-section, etc., as long as it has a cross-sectional area through which fine powder can pass. The grooves are arranged in a concentric shape, a grid shape, or the like on the sheet surface. The depth of the groove is 20 degrees, which depends on the thickness of the sheet, and ranges from 0.4 mm to 0.8 band. The polishing method of the semiconductor wafer of the present invention can be performed by using a known polishing machine and installing the polishing pad of the present invention. The polishing agent to be supplied between the polishing layer and the semiconductor wafer during polishing is not limited, and a known polishing agent used for polishing semiconductor wafers can be used. Specifically, abrasives such as thorium dioxide 53 1222390 thallium, description of the invention, and silicon dioxide can be used as examples. It is also suitable to use a commercially available product such as the abrasive SemiSperse-12 (manufactured by Cabot). Examples Hereinafter, the present invention will be described in more detail through examples, but the present invention is not particularly limited to the scope of these examples. [Examples 1 to 3] < Evaluation method >

(Evaluation of polishing characteristics) SPP600S manufactured by Okamoto Machine Tool Co., Ltd. was used as a polishing device, and 10 was used for evaluation of polishing characteristics. For the measurement of the oxide film thickness, an interference-type film thickness measuring device manufactured by Otsuka Electronics Co., Ltd. was used. The polishing conditions were such that a polishing liquid SemiSperse-12 (produced by Cabot Corporation) was dropped at a rate of 150 ml / min as a chemical liquid. The polishing load was 350 g / cm 2, the number of rotations of the polishing turntable was 35 rpm, and the number of rotations of the wafer was 30 rpm.

15 Evaluation of polishing characteristics. After depositing a 0.5 μm thermal oxide film on an 8-inch silicon wafer, the following patterning (lines / gap of 270/30 and 30/270) was performed, and then 1 μm of oxidization was deposited with p-TEOS. Film, and a wafer with a pattern having an initial drop of 0.5 μm was produced, and the wafer was polished under the aforementioned conditions. After the polishing, each drop was measured and the planarization characteristics were evaluated. The flattening characteristics were evaluated for two differences. One is a local drop, which is the drop of a pattern with a line of 270 μm wide arranged at a gap of 30 μm, and the other checks the grinding amount of the bottom of the gap of a line with a width of 30 μm arranged at a gap of 270 μm. The average polishing rate is an average polishing rate based on the average value of the line portion of 270 µm and the line portion of 30 µm. 54 1222390 发明 Description of the invention (Evaluation of the number of air bubbles) The measurement of the number of air bubbles is obtained by cutting the section of the obtained foamed abrasive layer with a microtome (test piece size: 5 mm x 5 mm) and section (measurement area: 0.45 deleted χ〇 · 67 legs) 200 times the microscope image by the image processing device image 5 analyzer V10 (manufactured by Toyo Textile Co., Ltd.) to separate the bubbles, and measure the number of bubbles per unit area and the bubble particle size distribution. In addition, the detection limit of bubbles is Ιμηι 〇 (Evaluation of average bubble diameter) The average bubble diameter is measured by cutting the obtained foamed abrasive layer with a 10-piece machine to cut out the cross-section, and using a microscope image of 200 times the cross-section to borrow the image The processing device image analyzer V10 (manufactured by Toyobo Co., Ltd.) separates bubbles, measures the particle size distribution of the bubbles per unit area, and calculates the average bubble diameter. (Compression ratio evaluation)

15 The compression ratio was measured by using a cylindrical indenter with a diameter of 5 mm and a tma manufactured by MAC SCIENCE at a temperature of 25 ° C on a foamed abrasive layer (sample size was 7 mm in diameter). μη), T2 (μηι) ο Compression ratio (%) = [(Τ1-Τ2) / Τ1] χ100 20 Wherein, T1 means the stress of the polishing layer from the unloaded state to a load of 30kPa (300g / cm2) and maintained The thickness of the layer at 60 seconds, T2 means the stress from the state of T1 to a load of 80 kPa and maintained at the thickness of 60 seconds. (D hardness measurement method) 55 1222390 玖, description of the invention This item is measured in accordance with JIS K6253. The abrasive layer cut to a thickness of 1.27 was cut into 6 pieces at an angle of 1.5 cm. After cutting out the specimens to maintain 23.5 degrees ± 2 ° Cx humidity 50% x 16 hours, 6 pieces of specimens were stacked and fixed on a D hardness tester. After piercing the D hardness tester with 65 or 5 stacked samples, read the D hardness tester pointer after 1 minute. (Measurement of storage elastic modulus)

The storage elastic modulus was measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM), a sine wave vibration was applied using a tensile test fixture, and the measurement was performed at a frequency of 1 Hz. Measured in temperature-dependent mode from 10-20 ° C to 80 ° C, and use storage elastic modulus at 40 ° C as elastic modulus (evaluation of uniformity)

An interference-type film thickness measuring device was used to measure the film thickness of 20 places on the polished surface of the polished silicon wafer with an oxide film. Using the maximum 15 Rmax and minimum Rmin of the film thickness, the uniformity (%) was calculated by the following formula. Uniformity (%) = (Rmax — Rmin) / (Rmax + Rmin)

x100 (quantitative method of the surfactant) Measure 15 mg of the polishing pad, and dissolve the polishing pad in 130 ° C at 0.7 ° C. The solution was centrifuged to settle, and 5 mg of tetrachloroethane was added to the supernatant solution, and a proton-NMR (proton-NMR, Bruker, AVANCE-500, 500 MHz) was used at a measurement temperature of 80 ° C and a detection pulse of 15 °. , Measure the spectrum under the conditions of FID injection time of 4 seconds, repeated time of 9 seconds, and measurement range of -2ppm ~ 14ppm. In addition, there is no need to use 56 1222390 (Invention Explanation) Window function in Fourier transform. The content of the surfactant was quantified from the area of the peaks obtained in the vicinity of & yin and the peaks obtained based on the four gas sintering and the nearby peaks obtained based on the methyl group combined with M). 5 [Example 1] (Example 1-1) 300 parts by weight of a polyamine urethane prepolymer (AdiPreneL-325, manufactured by Uniroyal) was placed in a trough. 120 parts by weight of a silica-based surfactant SH192 (dioxolithium polyoxyalkylene glycol copolymer 10 manufactured by Toray Dow Corning Silicone Co., Ltd.), and stirred with a mixer at about 90 rpm to prepare a foaming solution (bubble dispersion) Liquid), and then the mixer was replaced and put into a foaming solution while stirring 770 parts by weight of 4,4, fluorenyl-bis (2-aniline) which was melted as a hardener. After stirring for about 丨 minutes, the mixed solution was poured into a disc-shaped open mold, and was subjected to secondary hardening with a heating furnace at 6 ° C for 6 to 15 hours to form a foamed polyurethane block. The obtained foamed polyurethane was The number of bubbles of the acid ester is 350 / mm 2, the ASKER D hardness is 52, the compression ratio is 2.0%, the storage elastic modulus is 279Mpa, the specific gravity is 0.8, and the average bubble diameter is 40 μm. The polyurethane foam block is heated to about 50 ° C, and it is cut into a thickness of 127 by a 20-piece cutting machine VGW-125 (manufactured by AMITEC) to obtain a polishing pad. Its soft layer is used for one order. Non-woven fabric with 3.5 denier polyester fiber and a basis weight of 200 g / m2 is impregnated with 30% by weight of water-dispersed polyurethane emulsion and dried. The compression ratio of the non-woven layer is about 15%. This 57 57发明 Description of the invention The woven fabric is double-sided tape double tack tape # 5782 (manufactured by Sekisui Chemical Industry Co., Ltd.) and the previously manufactured abrasive layer is bonded, and a double-sided tape double tack tape # 5782 (Sekisui Chemical Industry Co., Ltd.) Company), the polishing pad is completed. The structure of the obtained polishing pad is shown in Figure 2. Thumbnail 5 ° (Examples 1-2)

The addition amount of the polysiloxane-based surfactant SH-192 of Example 1-1 was changed to 50 parts by weight, and the remaining parts were prepared in the same manner as in Example 1 to produce a polishing pad. The number of bubbles of the obtained foamed polyurethane was 230 per second, the hardness measured at 10 D was 58, the compression ratio was 1.4%, the storage modulus was 295 MPa, the specific gravity was 0.87, and the average bubble diameter was 35 μm. Further, when elemental analysis was performed by fluorescent X-rays, it was confirmed that Si was detected and that it contained a predetermined surfactant. (Examples 1-3)

15 Adhere double tack tape # 5782 to the abrasive layer prepared in Example 1-1, and paste the layer with low modulus of elasticity described later. The lower soft layer is a polyethylene foam having a foaming ratio of 10 times. The compression ratio of this foam layer is about 10%. The foam is bonded to the previously prepared abrasive layer with a double-sided tape, and then double tack tape # 5782 is pasted on the foam, and the 20 polishing pad is completed. (Examples 1-4) Double tack tape # 5782 was adhered to the abrasive layer prepared in Examples 1-2, and a layer with a low post-elastic modulus was affixed. The soft layer of the lower layer is a polyurethane foam having a foaming ratio of 15 times. The pressure of the foam layer 58 1222390 玖, the description of the invention, the shrinkage rate is about 12%. The foam was bonded to the previously prepared abrasive layer with a double-sided tape, and then a dot tack tape # 5782 was pasted on the foam to complete the grinding process. (Comparative Example 1-1) 5 The addition amount of the polylithium oxygen-based surfactant in Example 1-1 was changed to 1.4 parts by weight, and the remaining parts were prepared in the same manner as in Example 丨 to prepare a polishing pad. The resulting foamed polyurethane cannot form bubbles smoothly, and its amount is very small. In addition, its physical properties were 110 bubbles / mm 2, d hardness was measured as go, compression ratio was 1.0%, storage elastic modulus was 302 MPa, specific gravity was 0.91, and average gas bubble diameter was 65 μm. (Comparative Examples 1 to 2) The addition amount of the polysiloxane-based surfactant of Example 1-1 was changed to 100 parts by weight. In order to generate more bubbles, hollow resin particles (5 μm in diameter of Matsumoto grease) were added. The rest of the polishing pads were fabricated in the same manner as in Example i. At this time, large bubbles are generated during stirring. In addition, its physical properties were 850 bubbles / mm 2, D hardness was measured at 45, compression ratio was 2.3%, storage elastic modulus was 255 MPa, specific gravity was 0.70, and average bubble diameter was 25 μm. (Comparative Examples 1 to 3) The addition amount of the polysiloxane-based surfactant of Example 1 to 1 was changed to 250,000 serious scratches, and the rest was produced in the same manner as in Example 1. At this time, fine bubbles are evenly produced. Its physical properties are 700 bubbles per leg 2, D hardness is measured as 52, compression ratio is 5.2%, storage elastic modulus is 105 MPa, specific gravity is 0.45, and average bubble diameter is 25 μηι. . (Comparative Examples 1-4) 59 1222390 发明, description of the invention Double-tack tape # 5782 was pasted on the abrasive layer prepared in Comparative Examples 1-1, and a layer with a low modulus of postscript was affixed. The soft layer of the lower layer is a polyurethane foam having a foaming ratio of 15 times. The compression ratio of this foam layer is about 12%. Further, double tack tape # 5782 5 was stuck on the foam to complete the polishing pad. [Table 1] Number of bubbles Bubble diameter D Hardness Compression ratio Storage modulus Modulus Uniformity Lamination rate Flatten Other (μηι) (%) (Mpa) (%) (A / min) Example 1-1 350 38 52 2.0 279 4 Non-woven 2000 ◎ Example 1-2 230 45 58 1.4 295 9 Single layer 1600 ◎ Example 1-3 350 37 52 2.0 279 3 Polyethylene 2000 〇 Example 1-4 230 47 58 1.4 295 5 Urethane 1900 〇 Comparative Example 1-1 110 65 60 1.0 302 6 Single layer 800 to 1500 〇 Abrasive rate unstable Comparative Example 1-2 850 25 45 2.3 255 5 Single layer 900 to 1600 Δ Abrasive rate unstable Comparative Example 1-3 700 28 30 5.2 105 5 Single layer 1000 ~ 1500 X Unstable polishing rate Comparative Example 1-4 110 66 60 1.0 302 6 Urethane 700 Δ

[Evaluation Results] The evaluation results and characteristics are shown in Table 1. As can be seen from Table 1, when the polishing pads of Examples 1-1 to 1-4 were used, the polishing rate was largely stable, the uniformity was also good at less than 10%, and the planarization characteristics were also extremely excellent. In contrast, in the polishing pads of Comparative Examples 1-1, the polishing rate was unstable and the measurement was changed dramatically each time. In the polishing pads of Comparative Examples 1 to 2, the uniformity was 10% or less. Good 60 1222390 玖, the description of the invention is good, but the polishing rate is unstable and the planarization characteristics are slightly deteriorated. The polishing pads of Comparative Examples 1 to 3 also had a good uniformity of 10% or less, but the polishing rate was unstable and the planarization characteristics were significantly deteriorated. The polishing pads of Comparative Examples 1 to 4 had excellent planarization characteristics, but there were many scratches and the deterioration of the uniformity was more than 10%, and the polishing rate was also slightly lower. [Example 2] (Example 2-1)

Put 300 parts by weight of a polyether urethane prepolymer (AdipreneL-325, manufactured by UNIRO) into a container, and a polysiloxane-based surfactant 10 SH192 (dimethylsiloxane · polyoxyalkylene dioxide) Toray Dow Corning

120 parts by weight of Silicone Co., Ltd., and stirred with a stirrer at about 900 rpm to prepare a bubble dispersion. Thereafter, the stirrer was replaced while stirring 770 parts by weight of 4,4'-arylene-bis (2-chloroaniline). Put into bubble dispersion. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold, and heated in a 15-furnace furnace at 110 ° C for 6 hours for secondary hardening to form a foamed polyurethane block. The obtained foamed polyurethane had an ASKER D hardness of 52, a compression ratio of 2.0%, a storage elastic modulus of 279 MPa, a specific gravity of 0.8, and an average cell diameter of 40 µm. Subsequently, the foamed polyurethane block was heated to about 50 ° C, and cut into a thickness of 1.27 mm by a 20-piece cutting machine VGW-125 (manufactured by AMITEC) to obtain a polishing pad. Secondly, the soft layer is made of 3.5% denier polyester fiber and a non-woven fabric with a basis weight of 200 g / m2 impregnated with 30% by weight of a water-dispersed polyurethane emulsion and dried. The non-woven layer has a compression ratio of about 15%. This non-61 1222390 发明, invention description woven fabric is double-sided tape double tack tape # 5782 (manufactured by Sekisui Chemical Industry Co., Ltd.) and the previously prepared abrasive layer, and a double tack tape # 5782 is pasted on the non-woven fabric Finish the polishing pad. The schematic diagram of the structure of the obtained polishing pad is shown in FIG. The polishing pad 8 has a polishing layer 9 and a buffer layer 5 10. The polishing layer 9 and the buffer layer 10 are laminated with a double-sided tape 11 and a double-sided surface is provided on the buffer layer 10 for mounting on a polishing machine. Adhesive tape layer 12. (Example 2-2) The interfacial active dose of Example 2-1 was changed to 40 parts by weight, and more than 10 parts thereof were manufactured in the same manner as in Example 2-1 to make a polishing pad. The hardness of the obtained foamed polyurethane D was 59, the compression ratio was 1.3%, and the storage elastic modulus was 299 MPa, the specific gravity was 0.85, and the average cell diameter was 55 µm. (Example 2_3) The interfacial active dose of Example 2-1 was changed to 180 parts by weight, and the remaining 15 or more were manufactured in the same manner as in Example 2-1. The hardness of the obtained foamed polyurethane D was 47, the compression ratio was 2.4%, the storage elastic modulus was 272 MPa, the specific gravity was 0.78, and the average cell diameter was 34 µm. (Example 2-4) Double tack 20 tape # 5782 was stuck on the abrasive layer prepared in Example 2-1, and a buffer layer with a low elastic modulus was affixed. The buffer layer is made of a polyethylene foam having a foaming ratio of 10 times. The compression ratio of the foam layer is about 10%. The foam was bonded to the previously prepared abrasive layer with a double-sided tape, and then double tack tape # 5782 was pasted on the foam to complete the polishing pad. 62 1222390 发明 Description of the invention (Example 2-5)

Double tack tape # 5782 was adhered to the abrasive layer prepared in Example 2-2, and a buffer layer with a low elastic modulus was attached. The soft buffer layer was made by impregnating a 30% by weight water-dispersed polyurethane emulsion with a nonwoven fabric with 3.5 denier polyester fibers and a basis weight of 200 g / m 2 5 and drying. The non-woven layer has a compression ratio of about 15%. The non-woven fabric was bonded with the previously-adhered double-sided adhesive tape to the previously prepared abrasive layer, and a double-sided adhesive tape double tack tape # 5673FW (manufactured by Sekisui Chemical Industry Co., Ltd.) was pasted on the non-woven fabric to complete the polishing pad. The adhesive strength of each layer bonded by double-sided tape is 10 600 g / cm or more. (Example 2-6)

Double tack tape # 5782 was stuck on the abrasive layer prepared in Example 2-3, and a buffer layer with a low elastic modulus was stuck. The flexible buffer layer is a polyurethane foam having a foaming ratio of 15 times. The foam layer has a compression ratio of about 12%. The foam was bonded to the previously prepared abrasive layer with a double-sided tape, and then double tack tape # 5782 was pasted on the foam to complete the polishing pad. (Comparative Example 2-1) The interfacial active dose of Example 2-1 was changed to 1.0 part by weight, and more than 20 parts thereof were fabricated in the same manner as in Example 2-1. In addition, its physical properties were 62 with a D hardness measured, a compression ratio of 0.9%, a storage elastic modulus of 310 MPa, a specific gravity of 0.9, and an average bubble diameter of 80 μm. (Comparison Example 2-2) The interfacial active dose of Example 2-1 was changed to 500 parts by weight, which was 63 1222390 玖. Description of the invention The rest was made in the same manner as in Example 2-1. At this time, fine bubbles can be generated in the sentence. Its physical properties are measured as D hardness of 30, compression ratio of 5.2%, storage elastic modulus of 105 MPa, specific gravity of 0.45, and average bubble diameter of 25 μm 〇 5 (compared to the example of the vehicle delivery 2-3)

A double tack tape # 5782 'was stuck on the abrasive layer prepared in Comparative Example 2-1, and a buffer layer having a low elastic modulus was stuck. The soft buffer layer is a polyethylene foam having a foaming ratio of 10 times. The compression ratio of the foam layer is about 10%. The foam is bonded to the previously prepared abrasive layer with a double-sided tape and then double tack tape # 5782 is pasted on the foam to complete the polishing pad. (Comparative Examples 2 to 4)

Double tack tape # 5782 was stuck on the abrasive layer prepared in Comparative Examples 2-2, and a buffer layer with a low elastic modulus was stuck. The soft buffer layer 15 is made by impregnating a 30% by weight water-dispersed polyurethane emulsion with a nonwoven fabric with 3.5 denier polyester fibers and a basis weight of 200 g / m2. . The non-woven layer has a compression ratio of about 15%. The non-woven fabric is bonded with the previously-adhered double-sided tape to the previously made abrasive layer, and a double tack tape # 5673FW is pasted on the non-woven fabric to complete the polishing pad. The adhesive strength of each layer bonded by the double-sided tape 20 is 600 g / cm or more. 64 1222390 发明, Description of invention [Table 2]

Average bubble diameter (μηι) Number of bubbles D Hardness compression ratio (%) Storage modulus (Mpa) Uniformity (%) Lamination rate (A / min) Planarization Other Examples 2-1 40 360 52 2.0 279 4 Non-woven fabric 2000 ◎ Example 2 — 2 55 240 59 1.3 299 9 Single layer 1600 ◎ Example 2-3 34 380 47 2.4 272 4 Single layer 2000 〇 Example 2-4 40 350 52 2.0 279 3 Polyethylene 2000 〇 Example 2 -5 55 245 59 1.3 299 5 Non-woven cloth 1900 〇 Example 2-6 34 370 47 2.4 272 3 Urethane 2200 〇 Comparative Example 2-1 80 100 62 0.9 310 12 Single layer 800 ~ 1500 ◎ Comparison of unstable polishing rate Example 2-2 25 860 30 5.2 105 4 Single layer 900 ~ 1600 Δ Abrasive rate is unstable Comparative Example 2-3 80 95 62 0.9 310 8 Polyethylene 1550 〇 Comparative Example 2-4 25 850 30 5.2 105 3 Non-woven 1650 X

[Evaluation results]

The evaluation results and characteristics are shown in Table 2. When the polishing pads of Examples 2-1 to 2-6 were used, the polishing rate was largely stable, the uniformity was also good at 10% or less, and the planarization characteristics were extremely excellent. On the other hand, although the polishing pads of Comparative Example 2-1 had good planarization characteristics, the polishing rate was low and unstable, so that each measurement changed drastically. Although the polishing pads of Comparative Examples 2 to 2 had good uniformity of 10% or less, the polishing rate was low and unstable, and the planarization characteristics were significantly deteriorated. The polishing pads of Comparative Examples 2 to 3 had good flatness characteristics, but the polishing rate was slightly lower, and the average sentence was about 8%, which was slightly bad. The polishing pads of Comparative Examples 2 to 4 had very good planarization characteristics, but the polishing rate was 65 1222390 玖, the description of the invention was slightly low and the planarization characteristics were extremely poor. [Example 3] (Example 3-1)

Put 300 parts by weight of a polyether urethane prepolymer (AdipreneL-325, manufactured by Unilo 5) into a container, and a polysiloxane-based surfactant SH-192 (dihydrazine-polyoxygen 120 parts by weight of olefin diol copolymer manufactured by Toray Dow Corning Silicone Co., Ltd., and stirred with a stirrer at about 900i: pm to prepare a foaming solution (bubble dispersion), and then the stirrer was replaced and the stirring process was melted as a hardening agent. 4'-methylene-bis (2-gasaniline) 770 was added to the foaming solution in 10 parts by weight. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C for 6 hours by a heating furnace to produce a foamed polyurethane block. The obtained foamed polyurethane has a number of bubbles of 350 / mm 2, an ASKER D hardness of 52, a compression rate of 2.0%, a storage elastic modulus of 279 MPa, a specific gravity of 0.8, and an average bubble diameter of 40 μηι . In addition, when analyzing the content of the surfactant, it was confirmed that it contained about 3% by weight. Next, the foamed polyurethane block was heated to about 50 ° C, and was cut into a thickness by a microtome VGW-125 (manufactured by AMITEC). 1.27 nun to obtain a polishing pad. 20 Secondly, the soft layer is made by impregnating a non-woven fabric with 3.5 denier polyester fibers and a basis weight of 200 g / m2 impregnated with 30% by weight of a water-dispersed polyurethane emulsion and dried. The non-woven layer has a compression ratio of about 15%. The non-woven fabric was bonded with a double-sided tape double tack tape # 5782 (manufactured by Sekisui Chemical Industry Co., Ltd.) to a previously prepared abrasive layer, and a 66 1222390390, double-sided tape double tack tape # 5782 ( Sekisui Chemical Industry Co., Ltd.), the polishing pad is completed. The schematic diagram of the structure of the obtained polishing pad is shown in FIG. The polishing pad 8 has a polishing layer 9 and a buffer layer 10, and the polishing layer 9 and the buffer layer 10 are laminated with a double-sided tape 11 and a double layer 5 is provided on the buffer layer 10 for mounting on a polishing machine. Adhesive tape layer 12. (Example 2-3)

The addition amount of the polysiloxane-based surfactant SH-192 of Example 3-1 was changed to 40 parts by weight, and the rest were fabricated in the same manner as in Example 3-1. The number of bubbles of the obtained foamed polyurethane was 240 per leg 2 10, the D hardness was measured as 59, the compression ratio was 1.3%, the storage elastic modulus was 299 MPa, the specific gravity was 0.85, and the average bubble diameter was 55 μm. In addition, when the content of the surfactant was analyzed, it was confirmed that it contained about 1.0 wt%. (Examples 3 to 3)

The addition amount of the polysiloxane-based surfactant SH-192 in Example 3-1 was changed to 50 parts by weight, and the rest were fabricated in the same manner as in Example 3-1. The obtained foamed polyurethane has a number of bubbles of 230 cells / mm 2, a D hardness of 58, a compression rate of 1.4%, a storage elastic modulus of 295 MPa, a specific gravity of 0.87, and an average bubble diameter of 35 μm. In addition, when the content of the surfactant was analyzed, it was confirmed that it contained about 1.3% by weight. 20 (Example 3-4) The addition amount of the polysiloxane-based surfactant SH-192 of Example 3-1 was changed to 180 parts by weight, and the rest were fabricated in the same manner as in Example 3-1. The number of bubbles of the obtained foamed polyurethane was 380 cells / L 2, D hardness was measured as 47, compression ratio was 2.4%, storage elastic modulus was 272 MPa 67 1222390 玖, description of the invention, specific gravity 0.78 ′, average bubble diameter was 34 μm. In addition, when the content of the surfactant was analyzed, it was confirmed that it contained about 4.5% by weight. (Example 3-5) A double tack 5 tape # 5782 was stuck on the polishing layer prepared in Example 31, and a layer with a low elastic modulus was affixed. The soft layer of the lower layer is a polyethylene foam having a foaming ratio of 10 times. The compression ratio of the foam layer is about 10%. The foam was bonded to the previously prepared abrasive layer with a double-sided tape, and then double tack tape # 5782 was pasted on the foam to complete the polishing pad. 10 (Examples 3 to 6) Double tack tape # 5782 was adhered to the abrasive layer prepared in Examples 3 to 2, and a layer having a low elastic modulus was attached. The soft layer of the lower layer is a cloth made of 3.5 denier polyester fibers and having a basis weight of 200 g / m2 impregnated with 30% by weight of a water-dispersed polyurethane emulsion and dried. The compression ratio of the non-woven fabric layer is about 15%. The non-woven fabric was bonded with the previously-adhered double-sided adhesive tape to the previously manufactured abrasive layer, and a double-sided tape double tack tape # 5673FW (manufactured by Sekisui Chemical Industry Co., Ltd.) was pasted on the non-woven fabric to complete the polishing pad. (Examples 3 to 7) 20 On the abrasive layer prepared in Examples 3 to 3, double tack tape # 5782 was pasted, and a layer with a low elastic modulus was pasted. As the lower soft layer, a polyurethane foam having a foaming ratio of 15 times was used. The compression ratio of this foam layer is about 12%. This foam is bonded to the previously manufactured abrasive layer with a double-sided tape, and then double tack tape # 5782 is pasted on the foam. 68 1222390 玖, description of the invention polishing pad. (Examples 3 to 8)

Double tack tape # 5782 was adhered to the abrasive layers prepared in Examples 3-4, and a layer with a low elastic modulus was attached. The soft layer of the lower layer is a polyurethane foam having a foaming ratio of 15 times. The compression ratio of this foam layer is about 12%. The foam is bonded to the previously prepared abrasive layer with a double-sided tape, and then double tack tape # 5782 is pasted on the foam to complete the polishing pad. (Comparative Example 3-1) 10 The addition amount of the polysiloxane surfactant in Example 3-1 was changed to

1.0 part by weight, and the rest were fabricated in the same manner as in Example 3-1. The obtained foamed polyurethane did not form bubbles smoothly, and its amount was small. In addition, its physical properties were 100 bubbles per leg 2 and D hardness was measured at 62, compression ratio was 0.9%, storage elastic modulus was 310 MPa, specific gravity was 0.9, and average gas bubble diameter was 80 μm. In addition, when the content of the surfactant was analyzed, it was confirmed that it contained about 0.03% by weight. 0 (Comparative Example 2-3) The amount of the polylithium oxygen-based surfactant of Example 3-1 was changed to 1.4 parts by weight, and the rest were In the same manner as in Example 3-1, a grinding pad of 20 was manufactured. The resulting foamed polyurethane did not form bubbles smoothly, and its amount was very small. In addition, its physical properties were 110 bubbles per leg 2 and D hardness was measured at 60, compression ratio was 1.0%, storage elastic modulus was 302 MPa, specific gravity was 0.91, and average bubble diameter was 65 µm. In addition, when analyzing the content of the surfactant, it was confirmed that it contained about 0.04 wt%. 69 1222390 发明 Description of the invention (Comparative Examples 3 to 3) The addition amount of the polysiloxane surfactant in Example 3-1 was changed to 100 parts by weight, and hollow resin particles were added to generate more bubbles ( · Matsumoto Grease, 5 μm in diameter). The rest were fabricated in the same manner as in Example 3-i. At this time, larger bubbles may be generated during stirring. In addition, its physical properties were 850 bubbles / L2, D hardness was measured at 45, compression ratio was 2.3%, storage modulus was 255 MPa, specific gravity was 0.70, and average bubble diameter was 25 μm. In addition, when analyzing the content of the surfactant, it was confirmed that it contained about 26% by weight. (Comparative Example 3-4) The added amount of the polylithic oxygen-based surfactant in Example 3-1 was changed to 5000 parts by weight, and the rest were ground in the same manner as in Example 3-1. private school. Fine bubbles can be generated uniformly at this time. Its physical properties are 700 bubbles / L’ D hardness measured as 30, compression ratio 5.2%, storage modulus of elasticity 105 MPa ′ specific gravity 0.45 ′, average bubble straight pinch. In addition, when analyzing the content of 15 surfactants, it was confirmed that it contained about 12 ul. (Comparative Examples 3 to 5) _; A double tack tape # 5782 'was pasted on the abrasive layer prepared in Comparative Example 31 and a layer having a low elastic modulus was pasted. The soft layer of the lower layer is a polyurethane foam having a foaming ratio of 1 (3 times. The compression ratio of the foam layer is about 10/0 °, and a duo tack tape is pasted on the foam. # 5782, the polishing pad is completed. (Comparative Examples 3 to 6) On the polishing layer prepared in Comparative Example 32, paste double tack tape # 5782 'and attach a layer with a low elastic modulus. The softness of the lower layer The layer is made of 70 1222390 发明, a polyurethane foam with a foaming ratio of 15 times as described in the invention. The foam layer has a compression ratio of about 12%. Then double tack tape # 5782 is pasted on the foam. Then, the polishing pad is completed. (Comparative Examples 3 to 7) 5 A double tack is stuck on the polishing layers prepared in Comparative Examples 3 to 4.

tape # 5782, and paste the layer with low elastic modulus. The soft layer of the lower layer is a cloth made of 3.5 denier polyester fibers and having a basis weight of 200 g / m2 impregnated with 30% by weight of a water-dispersed polyurethane emulsion and dried. The non-woven fabric has a compression ratio of about 15%. The non-woven fabric was bonded with the previously-adhered double-sided adhesive tape 10 to the previously prepared abrasive layer, and a double-sided tape double tack tape # 5673FW (manufactured by Sekisui Chemical Industry Co., Ltd.) was adhered to the non-woven fabric to complete the polishing pad. 71 20 1222390 发明, Description of invention [Table 3]

Number of bubbles Average bubble diameter D Hardness compression ratio (%) Storage modulus (Mpa) Uniformity (%) Surfactant content (wt%) Lamination rate (person / min) Flattening Other Examples 3-1 350 40 52 2.0 279 4 3 Non-woven 2000 ◎ Example 3-2 240 55 59 1.3 299 9 1 Single layer 1600 ◎ Example 3-3 230 35 58 1.4 295 9 1.3 Single layer 1600 ◎ Example 3-4 380 34 47 2.4 272 4 4.5 Single layer 2000 〇 Example 3 — 5 350 40 52 2.0 279 3 3 Polyethylene 2000 〇 Example 3 — 6 245 55 59 1.3 299 5 1 Non-woven 1900 〇 Example 3 — 7 230 47 58 1.4 295 5 1.3 Amine Ethyl formate 1900 〇 Example 3 — 8 370 34 47 2.4 272 3 4.5 Ethyl urethane 2200 〇 Comparative example 3-1 100 80 62 0.9 310 12 0.03 Single layer 800 to 1500 ◎ Comparative example 3-2 110 65 60 1.0 302 6 0.04 Single layer 800 to 1500 〇 Comparative example of unstable polishing rate 3-3 850 25 45 2.3 255 5 2.6 Single layer 900 to 1600 Δ Comparative example of unstable polishing rate 3 — 4 700 28 30 5.2 105 5 12 Single layer 1000 to 1500 X Unstable polishing rate Comparative Example 3 -5 95 80 62 0.9 310 8 0.03 Polyethylene 1550 〇 Comparative example 3-6 110 66 60 1.0 302 6 0.04 Ethyl urethane 700 Δ Comparative example 3-7 700 25 30 5.2 105 3 12 Non-woven 1650 X

[Evaluation Results] The evaluation results and characteristics are shown in Table 3. When the polishing pads of Examples 3-1 to 3-8 were used, the polishing rate was largely stable, the uniformity was also good at 10% or less, and the planarization characteristics were extremely excellent. On the other hand, although the polishing pads of Comparative Examples 3-1 had good planarization characteristics, the research 72 1222390 发明, description of the invention, the polishing rate is low and unstable, so that each measurement changes dramatically. In the polishing pads of Comparative Examples 3 and 2, the polishing rate was unstable and the measurement changes sharply each time. Although the polishing pads of Comparative Examples 3 to 3 had good uniformity of 10% or less, the polishing rate was unstable and the planarization characteristics were slightly deteriorated. The polishing pad planarization characteristics 5 of Comparative Examples 3 to 4 were significantly deteriorated. The polishing pads of Comparative Examples 3 to 5 had good planarization characteristics, but the polishing rate was slightly lower, and the uniformity was also about 8%. The polishing pads of Comparative Examples 3 to 6 had poor planarization characteristics and low polishing rates. The polishing pads of Comparative Examples 3 to 7 had very good planarization characteristics, but the polishing rate was slightly low and the planarization characteristics were extremely poor. · [Example 4] 10 < Evaluation method > (Heat dimensional change rate) A measurement sample of 50 legs in length, 250 legs in width, and a thickness of 2 mm was cut out of the polishing layer constituent material, and held at 22.5t for more than 12 hours.敎 Longitudinal degree L. The measurement sample was held for 15 hours at a time, and the length in the longitudinal direction was measured. Find the difference between these lengths and use the following formula. · Thermal dimensional change rate = (AL / L) 100 × (%) (Compression ratio measurement method) The compression ratio measurement method is the same as the method described in Examples 1 to 3. 20 (Storage elastic modulus measurement method) The% storage elastic modulus measurement method is the same as the method described in Examples 1-3. Door (Xiao Er D hardness measurement method) Xiao Er D hardness measurement method is similar to the method described in Examples 1 to 3 73 1222390 玖, description of the invention 〇 (analysis of surfactant content) Analytical method of surfactant content and The methods described in Examples 1 to 3 are the same. .5 (Polishing characteristics) The polishing characteristics of the polishing pads were evaluated using a 6-inch silicon wafer with a thermal oxide film 1 μηι. After polishing for 5 minutes, the in-plane film thickness of the wafer was measured at 28 points. The in-plane uniformity obtained by the following formula is performed. The polishing characteristics were evaluated using a CMP polishing apparatus SPP-600S (manufactured by Okamoto Machine Tool Co., Ltd.). The polishing conditions were as follows: the silica slurry RD97001 (manufactured by Fujimi Incorporated), which was adjusted to pH 11 as a polishing liquid, was injected at a flow rate of 150 g / min, and the polishing load was 350 g / cm. 2. The polishing pad was rotated. The polishing was performed at 35 rpm and 33 rpm. 15 In-plane uniformity (%) = {(maximum film thickness-minimum film thickness) / (2x average film

Thick)} xlOO Those with in-plane uniformity of less than 10% were evaluated as good and marked as 0, those with 10% or more were evaluated as bad and marked as X. The planarization characteristic is that 20 μm of a thermal oxide film is deposited on an 8-inch silicon wafer, and a predetermined pattern is formed. Then, a 1 μm oxide film is deposited with p-TEOS, and a pattern with an initial drop of 0.5 μm is formed. The wafer was polished under the aforementioned conditions. After polishing, each drop was measured and the planarization characteristics were evaluated. Those with good planarization characteristics were evaluated as 0, and those with poor planarization characteristics were evaluated as X. (Example 4-1) 74 1222390 发明, description of the invention: 100 parts by weight of a polyether-based prepolymer (AdipreneL-325 manufactured by Uniro; the isocyanate group concentration of 2.22 meq / g) was mixed with a polysiloxane in a container. The nonionic surfactant SH792 was 1 part by weight (0.79% by weight based on the polyurethane), and was adjusted to 80 ° C. Here, while stirring vigorously to absorb air bubbles, 26 parts by weight of 4,4, amidino-bis (o-chloroaniline) (MOCA), which was previously melted, was added. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C. for 6 hours by a heating furnace to obtain a polyurethane resin foam block. The density of the obtained polyurethane resin foam block was 0.92 g / cm 3. 10 Use a slicer to cut out the foam sheet from the polyurethane resin foam block, and process the concentric grooves to make a polished surface, and laminate a commercially available non-woven cloth on the inside. The cushioning material formed by the polyurethane is crushed to make a grinding mill. (Example 4-2) 15 A polyurethane resin foam was prepared in the same manner as in Example 4-1, except that 3 parts by weight of SH192 was used as a polysiloxane nonionic surfactant. Into pieces. The density of this polyurethane resin foam block was 0.87 g / cm 3. From the obtained polyurethane resin foam block, 20 pieces of the foam sheet were cut out using a microtome, and a polishing pad was produced in the same manner as in Example 4-1. (Example 4-3) Toluene monoisocyanate (2,4-is / 2,6-is = 80/2/2 mixture: hereinafter referred to as TDI) 1480 parts by weight, 4,4, dicyclohexylmethane 393 parts by weight of diisocyanate (hereinafter referred to as HMDI), polytetramethylene glycol (Mn 75 1222390 玖, description of the invention: 818) 2145 parts by weight and 276 parts by weight of diethylene glycol are mixed, and heated and stirred at 80 ° C for 120 Minutes to prepare an isocyanate-terminated prepolymer (isocyanate group concentration 2.29 meq / g). The polyether prepolymer in Example 4-1 was changed to 100 parts by weight of the isocyanate 5-terminal prepolymer, and 6 parts by weight (4.51% by weight relative to polyurethane) of SH192 was used as the poly A siloxane-based nonionic surfactant, and 27 parts by weight of MOCA was used, and the rest was obtained in the same manner as in Example 1 to obtain a polyurethane resin foam block. The density of the agglomerates of the polyurethane resin foam was 0.81 g / cm 3. 10 Using a microtome, a foam sheet was cut out of the obtained polyurethane resin foam block, and a milled pad was produced in the same manner as in Example 4-1. (Examples 4 to 4) TDI (1730 parts by weight), HMDI (393 parts by weight), polytetramethylene glycol (Μη: 1006) 2515 parts by weight and diethylene glycol 276 parts by weight 15 were mixed and mixed at 80 The mixture was heated and stirred at ° C for 120 minutes to prepare an isocyanate-terminated prepolymer (isocyanate group concentration: 2.58 meq / g). The polyether-based prepolymer in Example 4-1 was changed to use 100 parts by weight of the isocyanate-terminated prepolymer, and 6 parts by weight (4.54% by weight relative to the polyurethane) of SH192 was used as the polysilicon. An oxygen-based nonionic interfacial active agent 20 was used in an amount of 24 parts by weight of MOCA and 2.3 parts by weight of glycerin was added. The rest was prepared in the same manner as in Example 4-1. Into pieces. The density of the block of the polyurethane resin foam was 0.72 g / cm 3. The obtained polyurethane resin foam block was cut with a microtome 76 1222390 玖, the foam sheet was described in the invention, and a polishing pad was prepared in the same manner as in Example 4-1. (Comparative Example 4-1) Except using 10 parts by weight of SH192 as a polysiloxane nonionic surfactant, the same procedure as in Example 4-1 was performed to obtain a poly (fluorene) -5 ester resin foam. Into pieces. The cost of this polyurethane resin foam block was 0.68 g / cm 3.

A foamed sheet was cut out of the obtained polyurethane resin foam block with a microtome, and a polishing pad was produced in the same manner as in Example 4-1. Polishing tests were performed on the polishing pads 10 prepared in Examples 4-1 to 4-4 and Comparative Example 4-1, and the planarization characteristics and in-plane uniformity were evaluated. The results are shown in Table 4. The content of the surfactant can be converted to the weight% relative to the purpose of the polyurethane S (prepolymer + chain extender).

Team

15 、 'σ clothing, the thermal dimensional change rate is within the scope of the present invention, and its flatness characteristics and in-plane uniformity are both good, but those whose thermal dimensions are beyond those of the present invention have flatness characteristics and in-plane uniformity. All of them are carbon. [Example 5] < Evaluation method > 20 (Dynamic friction coefficient measurement method) 77 1222390 发明 Description of the invention The measuring device for the dynamic friction coefficient is shown in FIG. 3. The third figure is a royal figure 'and the third figure (b) is a structural diagram of the measurement sample 19. FIG. The measurement system is a sheet 14 for constituting a polishing layer placed on a glass placed on a table 16 (high heat-resistant glass Pyrex Division (manufactured by Corning Corporation, # 7740, 15〇 prison 250 5 followed by 5111111)) 15 And double-sided tape (double tack tape # 5782, 20㈣ buffer layer (specific density 〇07 low-density polyethylene foam thickness · 1.27 coffee) 21, and then double-sided tape 535A (manufactured by Nitto Denko) ) 22 The buffer layer 21 is adhered to the coating layer to form a measurement sample 19 provided with the coating layer 13. Next, the abrasive layer of the measurement sample 19 is formed into a thin film by rubbing the measuring device 18 with a rubbing device 10. 14 On the glass plate, 'move in contact with the moon and force it to move in the direction of arrow 17 to measure the coefficient of friction. The coefficient of dynamic friction is shown in the graph of the friction force measured by the above-mentioned friction coefficient device' and the measurement sample 19 is moved 1 At 0 °, the average value of the minimum and maximum values of the dynamic frictional force after the 15 frictional force is calculated and divided by 44 kgf. · The size of the polishing layer constituent sheet is 5 cm x 8 cm, and the weight of the coating 13 for the load is 4.4kg, bottom surface is 8 cmx5⑽, measure the moving speed of sample 19 It is 20 cm / min and the measurement time is 30 seconds. The friction measuring device 19 series uses 20 TenS110n RTM-100 (manufactured by τ〇γ〇BALDWIN), and the environmental conditions are temperature (23 ± 2) ° C, humidity (50 ± 6)% RH. (Evaluation of polishing characteristics) Using SPP600S manufactured by Okamoto Machine Tool Co., Ltd. as the polishing device, the evaluation of 4T polishing characteristics is performed. The thickness of the oxide film is measured using Otsuka Electronics Corporation 78 1222390 The dry film thickness measuring device is manufactured. The polishing conditions are: the polishing load is 8; the number of rotations of the grinding wheel is 35 rPm; and the number of wafer rotations is 30 rpm / grinding. It was dripped at a flow rate of 150 ml / min during grinding. The grinding method was the same as that described in Example 3. (Compression ratio measurement method) The compression method was the same as the method described in Example 30. Lu ( Storage elastic modulus measurement method) 10 Storage elastic modulus method is the same as the method described in Example 3 0 (average bubble diameter measurement method) The average bubble diameter measurement method is the same as the method described in Example 3 0 15 (Xiao Er D hardness test (Determination method) Xiao Er D hardness measurement method is the same as the method described in Example ^ 0 (analysis of surfactant content) Analytical method for the content of surfactant is the same as the method described in Examples 1 to 3. (Example 5-1) Put a poly-ethyl urethane prepolymer (Adiprene L-325, manufactured by UNIRO) in a container in an amount of 3 ^, and a polylithium oxygen-based surfactant SH192 (Poly Methyllithium oxygen · polyoxyalkylene copolymer, Toray Dow Corning 79 1222390 (manufactured by Silicone Co., Ltd.) 120 parts by weight, and stirred with a mixer at about 900 rpm to make a foaming solution (bubble dispersion), and then replaced the mixer On the other hand, 770 parts by weight of the hardening agent (4,4'_methylene-bis [2-gas aniline]) heated and melted in the stirring industry was put into a foaming solution. After stirring for about 1 minute, the mixed 5 liquid was poured into a disc-shaped open mold, and was subjected to secondary hardening at 110 ° C for 6 hours by a heating furnace to obtain a foamed polyurethane block. The hardness and D hardness of the obtained foamed polyurethane were measured as 52, the compression ratio was 2.0%, the storage elastic modulus was 279 MPa, the specific gravity was 0.8, and the average bubble diameter was 40 μm. In addition, when the content of the surfactant was analyzed, It was confirmed to contain about 2.8 wt%. 10 Next, the foamed polyurethane block was heated to about 50 ° C and cut with a cutter VGW-125 (manufactured by AMITEC) to a thickness of 1.27 ram to obtain a polishing layer constituting a sheet. The buffer layer is prepared by impregnating a non-woven fabric with 3.5 denier polyester fibers and a basis weight of 200 g / m2 impregnated with 30% by weight of a water-dispersed polyurethane emulsion and dried. The buffer layer constituent material (thickness of 1.27 legs) was double-sided tape double tack tape # 5782 (manufactured by Sekisui Chemical Industry Co., Ltd.) and the previously prepared abrasive layer, and a double tack tape # 5782 was stuck on the buffer layer. Then grinding (a) is completed. Regarding the polyurethane foam 20 of the polishing layer constituting material of Example 5-1, the dynamic friction coefficient measured by the above method was 0.5. When the polishing pad (a) is used and polishing is performed under the above conditions, the polishing rate is 2300 persons / min, which is a sufficient polishing rate in terms of practicality. In addition, at this time, there is no case of missing items. (Example 5-2) 80 1222390 发明, description of the invention Except for adding 40 parts by weight of a polysiloxane surfactant SH192, the rest are all made in the same manner as in Example 5-1 to produce a foamed polyurethane composition. · Blocks. The hardness and D hardness of the obtained foamed polyurethane were measured at 59, the compression ratio was 1.3%, the storage elastic modulus was 299 MPa, the specific gravity was 0.85, and the average 5 bubbles were directly controlled to 55 μηι. In addition, when the content of the surfactant was analyzed, it was confirmed that the content was about 0.9% by weight. The coefficient of kinetic friction of the polyurethane foam of Example 5-2 was 0.3. · When using this polyurethane foam sheet and polishing pad (b) in the same manner as in Example 10, and polishing under the same conditions as in Example 5-1, the polishing rate was 2000 A / Min is a sufficient polishing rate in terms of practicality. In addition, at this time, there is no case of missing items. (Examples 5 to 3) Except that 180 parts by weight of a polysiloxane-based surfactant SH192 was added, the rest 15 were produced in the same manner as in Example 5 to 1 to produce a foamed polyurethane block. The hardness and D hardness of the obtained foamed polyurethane were measured to be 47, the compression ratio was 2.4%, the storage elastic modulus was 272 MPa, the specific gravity was 0.78, and the average cell diameter was 34 µm. In addition, when analyzing the content of the surfactant, it was confirmed that it contained about 4.4% by weight. 20 The dynamic friction coefficient of the polyurethane foam of Example 5-3 was determined to be 0.7. Using the sheet of the polyurethane foam, a polishing pad was prepared in the same manner as in Example 5-1 (c ), And when grinding was carried out under the same conditions as in Example 5-1, the grinding rate was 2600 persons / min, and in terms of practicality, it can be said to be 81 1222390 充, the grinding rate sufficient for the invention. In addition, at this time, there is no case of missing items. (Comparative Example 5-1) Using the non-foamed polyurethane produced in Example 51 without adding and stirring a surfactant, the kinetic friction coefficient was measured by the method described above to be 5.01. In addition, when polishing was performed with the non-foamed polyurethane, the polishing rate was as low as 1,000 A / min, and the purpose of high polishing rate could not be achieved. (Comparative Example 5-2) The added amount of the polysiloxane-based surfactant of Example 5-1 was changed to 1.4 parts by weight, and the remaining 10 pads were prepared in the same manner as in Example 5-1. The resulting foamed polyurethane did not form bubbles smoothly, and its amount was very high). Also, its physical properties are Xiao and D hardness is measured at 60, compression ratio is 1.0%, storage elastic modulus is 302 MPa, specific gravity is 0.91, and average bubble diameter is 65 μm. In addition, when the content of the surfactant was analyzed, it was confirmed that it contained about 0.003 wt%. The coefficient of kinetic friction of the polyurethane foam of Comparative Example 5-2 was 0.05. A polishing pad (c) was prepared in the same manner as in Example $ -1 using the sheet of the polyurethane foam, and the polishing rate was 12 when polishing was performed under the same conditions as in Example 5j. 〇A / min, can not achieve the purpose of high polishing rate. (Comparative Example 5-3) The addition amount of the poly dream oxygen-based surfactant of Example 5-1 was changed to 50 parts by weight, and the rest were fabricated in the same manner as in Example 5-1. At this time, fine bubbles can be generated in the homogram. The properties of the obtained foamed polyurethane were low and D hardness was measured as 30, the compression ratio was 5.2%, the storage elastic modulus was 105 MPa, the specific gravity was 0.45, and the average cell diameter was 25 μm. In addition, 82%, description of the invention When analyzing the content of the surfactant, it was confirmed that it contained about 115 wt0 / 0. The coefficient of kinetic friction of the polyurethane foams of Comparative Examples 5 to 3 was U. Using this polyurethane foam sheet, a polishing pad (c) was prepared in the same manner as in the example, and when polishing was performed under the same conditions as in Example 5-1, the polishing rate was 300 0 A / min. Although the grinding speed is good, it will cause the situation of getting lost. The results of the aggregate evaluation are shown in Table 5. 〔table 5〕

Addition amount of surfactant (parts by weight) Content of surfactant (wt%) Coefficient of dynamic friction D hardness compression rate (%) Storage modulus of elasticity grinding rate (A / min) Removal of clamping error Example 5-1 120 2.8 0.5 52 2.0 279 2300 〇 Example — 5-2 40 0.9 0.3 59 1.3 299 2000 〇 Example _ 5-3 180 4.4 0.7 47 2.4 272 2600 〇 Comparative Example 5-1 0 0 0.01 74 0.5 760 1000 〇 ^ 5-2 LU 7 «| 1.4 0.03 0.05 60 1.0 302 1200 〇 Example of dagger 5-3 500 11.5 1.2 30 5.2 105 3000 X or more, with polyurethane resin foam and dynamic coefficient of friction of 0.1 The polishing pad with a polishing layer of ~ 1.0 has a practical and sufficient polishing rate, and there is no occurrence of pinching. [Example 6] < Evaluation method > (Measurement of storage elastic modulus) The method of measuring the storage elastic modulus is the same as the method described in Examples 1 to 3 (the Xiao D hardness measurement method) the Xiao D hardness measurement The method is the same as the method described in Examples i to 3. 1222390 玖, description of the invention 0 (Compression ratio measurement method) The compression ratio measurement method is the same as the method described in Examples 1 to 3. (Measurement of Abrasion Loss) 5 The obtained polished layer was dried as a test piece and the initial weight was measured. The potassium hydroxide aqueous solution adjusted to pH 12 · 5 was adjusted to 40 ° C ', and the test piece was immersed therein for 24 hours, after which it was thoroughly washed with distilled water and then dried. The abrasion wheel abrasion tester (Model 174, manufactured by TABER) was used to measure the abrasion of the test piece before and after the test under the conditions of a load of 1000 g, abrasion wheel Η · 22, and 1000 rpm. The smaller the difference in abrasion loss, the better. (Production and Evaluation of Polishing Pad) A double-sided tape (manufactured by Sekisui Chemical Industry, double tack tape # 5782) was attached to the obtained polishing layer, and the polishing pad was completed. The polishing characteristics of the obtained polishing pad were evaluated using a CMP polishing apparatus (manufactured by Okamoto Machine Tool Co., Ltd., SPP-600S). The polishing conditions were as follows: the silicon dioxide slurry (Fujimi Incorporated, RD97001), which has been adjusted to pH 11 as a polishing liquid, was injected at a flow rate of 150 g / min, while the polishing load was 350 g / cm 2. The number of rotations of the polishing pad Polishing was performed at 35 rpm and wafer rotation number of 33 rpm. (Flatness) The evaluation of flatness is the patterning of L / S (line and gap) = 25μιη / 5μιη and 1 / s = Μ— after depositing a thermal oxide film of G on a 6 n-cut wafer. Furthermore, an oxide film (te0s) was deposited, 84 1222390 堆积, and the invention was described to produce a wafer having a pattern of an initial drop of 0.5 μm. The wafer was polished under the above-mentioned polishing conditions, and when the total drop was 2,000 or less, the bottom reduction of the 25 µm gap was measured and evaluated. The smaller the flatness, the better. 5 (In-plane uniformity) Evaluation of in-plane uniformity was performed by using a thermal oxide film 1 μm deposited on a 6-inch silicon wafer, and polishing under the above-mentioned polishing conditions until the thermal oxide film was 0.5 μm. The in-plane film thickness of a circle is 28 points, and the in-plane uniformity is obtained by the following formula. The smaller the value of the in-plane uniformity, the better the uniformity. 1〇 In-plane uniformity (%) = 丨 (maximum film thickness-minimum film thickness) / (2χ average film

Thick)} xlOO (average polishing rate) The average polishing rate is evaluated by using a thermal oxide film 1 μm deposited on a 6-inch silicon wafer and polishing under the above-mentioned polishing conditions. The value obtained by subtracting the film thickness after polishing divided by the current polishing time is the value obtained by evaluation. The larger the average grinding speed, the better. (Polishing speed stability) The polishing speed stability can be obtained by the following formula.

Polishing speed stability (%) = {(maximum polishing speed-minimum polishing speed) / average polishing speed 丨 x100 The maximum polishing speed indicated is from the first wafer to the number of processed wafers (100, 300, or 500) The maximum polishing rate between wafers, and the minimum polishing rate is the minimum polishing rate from the first wafer to the same number of wafers at the same time. (Example 6-1) Put 1,000 parts by weight of toluene diisocyanate (mixture of 2,4-is / 2,6-is = 80/20), 4,4, -dicyclohexyl methane di in a container 375 5 parts by weight of isocyanate, 1681 parts by weight of polytetramethylene glycol (number average molecular weight 994), and 188 parts by weight of diethylene glycol, and heated and stirred at 80 ° C. for 150 minutes to obtain an isocyanate equivalent weight of 2.28 meq / g Prepolymer. 97 parts by weight of a polysiloxane non-ionic surfactant (SH-192 manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to the prepolymer, and the temperature was adjusted to 10 7 ° C and vacuum degassing was performed. Then, while stirring vigorously to take in air bubbles, 943 parts by weight of 4,4, -methylene-bis (o-aniline) melted at 120 ° C was added in advance to prepare a mixed solution. After stirring for about 丨 minutes, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C. for 8 hours to obtain a block of a polyurethane microfoam (a pore size of 40 μm). The density of the polyurethane 15 microfoam agglomerates was 0.87 g / cm 3. The density was measured in accordance with JIS K 7222 (foamed plastics and rubbers, which is a measurement of apparent density). Next, the polyurethane microfoamed block was heated to about 80 ° C., and cut with a microtome (made by AMITEC Corporation, VGW-125) to a thickness of 1.27 to obtain a polishing layer. A strip with a width of 5 legs was cut out from the thin layer, and the storage elastic modulus was measured to be 285 MPa. The D hardness was 54 and the compression ratio was 1.5%. (Example 6-2) Put 1,000 parts by weight of 4,4, -dicyclohexylpyrane in a container into toluene diisocyanate (mixture of 2,4_is / 2,6-is = 80/20) Diisocyanate 146 86 1222390 玖, description of the invention, parts by weight, polytetramethylene glycol (number average molecular weight 796) 1150 parts by weight, 188 parts by weight of diethylene glycol, and heating and stirring at 80 ° C for 15 minutes to obtain an isocyanate Equivalent 2.29 meq / g of prepolymer. To this prepolymer was added 75 parts by weight of a polysilicone oxygen-based nonionic surfactant (5 'SH-192 manufactured by Toray Dow Corning Silicone Co., Ltd.), and the temperature was adjusted to 70 ° C and vacuum degassing was performed. Then, while stirring vigorously to take in air bubbles, 730 parts by weight of 4,4, -methylene-bis (o-chloroaniline) melted in advance at 120 ° C was added to prepare a mixed solution. After stirring for about i minutes, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C. for 8 hours to obtain a block of poly (urethane 10) microfoam (pore size: 35 μm). The density of the polyurethane microfoam agglomerates was 0.75 g / cm 3. In addition, in the same manner as in Example 6.1, a polishing layer and a polishing pad were prepared and evaluated for polishing. (Reference Example 6-1) 15 Put 1,000 parts by weight of 4,4, -dicyclohexylmethane in a container with toluene diisocyanate (mixture of 2,4-body / 2,6-body = 80/20) 375 parts by weight of diisocyanate, 1362 parts by weight of polyethylene adipate (number-average molecular weight 746), 188 parts by weight of diethylene glycol, and heating and stirring at 80 ° C for 150 minutes to obtain an isocyanate equivalent of 2.43 meq / g Prepolymer. 88 parts by weight of a polysiloxane-based nonionic surfactant (SH-192 manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to the prepolymer 20, and the temperature was adjusted to 70 ° C and vacuum degassing was performed. Then, while stirring vigorously to take in air bubbles, 903 parts by weight of 4,4'-methylene-bis (o-aniline) melted in advance at 120 ° C was added to prepare a mixed solution. After stirring for about 1 minute, the mixed solution was poured into an open mold cut into a plate of 87 1222390, and the invention was shaped into an open mold, and was subjected to secondary hardening at 110 ° C. for 8 hours to obtain a polyurethane micro foamed block ( 35 μm pore size). The density of the agglomerates of the polyurethane microfoam was 0.70 g / cm 3. In addition, in the same manner as in Example 6-1, a polishing layer and a polishing pad were prepared and evaluated for polishing. (Reference Example 6-2) Put 1,000 parts by weight of toluene diisocyanate (2,4-is / 2,6-is = 80/20 mixture), 4, 4, dicyclohexyl methane di 375 parts by weight of isocyanate, polyester polyol obtained by polymerizing phthalic anhydride and ethylene glycol (quantity: 10 average molecular weight: 1006), 1746 parts by weight, 188 parts by weight of diethylene glycol, and stirred at 80 C for 150 minutes. Isocyanate g prepolymer with an equivalent weight of 2.2 lmeq / g. 88 parts by weight of a polysiloxane-based nonionic surfactant (SH-192 manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to the prepolymer, and the temperature was adjusted to 70 ° C and vacuum degassing was performed. Next, while stirring vigorously for 15 to take in air bubbles, 930 parts by weight of 4,4, _methylene-bis (o-aniline) melted in advance at 120 ° C was added to prepare a mixed solution. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C for 8 hours to obtain a block of polyurethane microfoam (pore size 40 µm). The density of the polyurethane microfoam agglomerates was 0.84 g / cm 3. 20 In the same manner as in Example 6-1, a polishing layer and a polishing pad were prepared and evaluated for polishing. (Reference Example 6-3) In a container, 150 parts by weight of a polysiloxane-based nonionic surfactant (manufactured by Toray Dow Corning Silicone Co., Ltd., SH-192) was placed in Adiprene L-325 (iso 88 1222390). Description of the Invention

S-cyanate terminal prepolymer, NCO == 9.25% (produced by Yuerakuro Co.) in an amount of 1,000 parts by weight, and the temperature was adjusted to 70 ° C and vacuum degassing was performed. Next, while mixing vigorously to take in air bubbles, 250 parts by weight of 4,4'-methylene-bis (o-chloroaniline) which was previously melted at 120 ° C was added to prepare a mixed solution. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold, and subjected to secondary hardening at 110 ° C for 8 hours by a heating furnace to obtain a polyurethane microfoamed block (pore size: 35 µm). The density of the polyurethane microfoam agglomerates was 0.76 g / cm 3. In addition, in the same manner as in Example 6-1, a polishing layer and a polishing pad were prepared and evaluated for polishing. [Table 6] Abrasive rate Abrasive modulus of the polishing pad D Hardness compression ratio (%) Abrasion amount (mg) Flatness (A) In-plane uniformity Average polishing rate Stable polishing rate (%): Qualitative wafer number (Mpa ) Difference before test (%) (A / min) 100 300 300 500 Example 6-1 285 54 1.5 51 54 3 1000 7.5 1160 5 6 9 Example 6-2 292 56 1.3 66 74 8 900 7.9 1210 3 5 8 Reference example 6-1 311 59 0.9 55 69 14 900 8.3 1140 5 11 22 Reference example 6-1 278 53 1.8 43 60 17 900 7.2 1230 4 16 27 Reference example 6-1 235 38 3.9 49 54 5 1400 6.9 1310 6 8 11

From the results in Table 6, it can be seen that the polishing pad of the present invention is excellent in flatness and in-plane uniformity, and has a high polishing speed, and the stability of the polishing speed is also good. 'The polishing speed change from use to completion Very little, grinding characteristics are very stable. [Example 7] < Evaluation method > (Polishing characteristics) 89 1222390 玖 Description of the invention The polishing characteristics of the polishing pads were evaluated using a CMP polishing apparatus SPP-600S (manufactured by Okamoto Work Machinery Co., Ltd.). The grinding conditions were as follows: at a flow rate of 150 g / min, a rhenium oxide slurry (hafnium dioxide sol manufactured by Nissan Chemical Co., Ltd.) which had been adjusted to pH 8 as a grinding liquid was injected, and a grinding load of 350 g / cm 2 was used at the same time. The polishing was performed at 35 rpm and 33 rpm. The polishing characteristics were evaluated at an average polishing rate. If the polishing rate is 2000 A / min or more, the polishing characteristic is evaluated as 0, and if it is less than 200 A / min, the polishing characteristic is evaluated as X. (Monomer Residual Ratio) 10 Dissolve 10 mg of an isocyanate-terminated prepolymer obtained by inertizing a terminal isocyanate group with methanol in 10 ml of THF, and use a GPC measuring device LC10A (manufactured by Shimadzu Corporation) from an isocyanate monomer. The peak area of the methanol reactant was used to determine the monomer residual ratio. The measurement was performed using a Plgel chromatography tube (with a filler particle diameter of 5 μm and a pore size of 15 500/100/50 persons), a sample solution of 40 μb was injected, THF was used as a solvent, and the measurement was performed at a flow rate of 1 ml / min. (Usage time) The isocyanate-terminated prepolymer is heated to 60 ° C, and molten 4,4'-fluorenylenebis (o-chloroaniline) adjusted to 120 ° C is added and mixed to make 20 NCO group / 0H group equivalent. The ratio is 1.1, and the mixture is cast on a glass plate heated to 50 ° C to form a thickness of about 5 li. Poke the liquid film 3 times with a square rod (about 3 leg angles) and observe the surface for 10 seconds. The liquid has no fluidity and the concavities and convexities formed by the piercing by the angle stick remain after 10 seconds. (Formability evaluation) 90 1222390 发明 Description of the invention In the following manufacturing example of a polishing pad material, the result of forming a hardening foam composition into a disc-shaped open mold and molding the moldability was 0 when the mold was completely injected into the mold. The moldability was evaluated as X when it was not completely distributed in the mold. (Example 7-1 to 7-5, Comparative Example 7-1 to 7-6) 5 < Production of polishing pad material > Polytetramethylene glycol (hereinafter referred to as PTMG) having a number average molecular weight of 1,000 and Diethylene glycol (hereinafter referred to as DEG) is a mixture obtained by mixing PTMG / DEG = 50/50 (molar ratio) as a diol component, and the diol component and toluene diisocyanate (2,4-body / 2) , 6-body = 80/20 mixture: The following 10 is referred to as TDI) Excessive use to make the reaction TDI monomer reach a predetermined amount, and then heating and stirring at 80 ° C for 120 minutes, followed by vacuum distillation to remove the isocyanate monomer Isocyanate terminated TDI prepolymer. In addition, the same diol component was used and an excess of 4,4'-dicyclohexylpinene diisocyanate (hereinafter referred to as HMDI) was used to make the HMDI monomer 15 after the reaction reach a predetermined amount, and then heated and stirred at 80 ° C for 120 minutes. The isocyanate monomer was removed by vacuum distillation to prepare an isocyanate terminated HMDI prepolymer. The two types of prepolymers are mixed so that the weight ratio of TDI prepolymer / HMDI prepolymer reaches 75/25, and further each isocyanate monomer is added so that each isocyanate monomer reaches a predetermined amount, and foamed polyurethane is formed. The raw materials for the manufacture of esters are pre-polymerized. A predetermined amount of a polysiloxane-based surfactant SH-192 (manufactured by Toray Dow Corning) was added to 100 parts by weight of the obtained raw material prepolymer and mixed. After adjusting to 80 ° C, a stirring blade having a whipping type was used. The stirrer was vigorously stirred to take in air bubbles to prepare a bubble dispersion. The stirring device was changed to planetary 91 1222390 玖, an invention-type agitator, and the bubble dispersion was added in advance by 12 (rc melted 4.4-methylene bis (o-aniline) (hereinafter referred to as)). NCO / NH2 when the ratio is 达 · ι, and mixed for about i minutes. The obtained curable foaming composition is put into a disc-shaped open mold, and it is heated for 5 hours and 6 hours by 110 ° with a heating furnace. After secondary hardening, a foamed polyurethane block is produced. The foam of the foamed polyurethane is about 40 μm to 50 μm, and the density is 〇85g / cm 3 to 〇.90g / cm 3. Prepolymer The residual ratio of isocyanate monomer and the HMDI monomer / TDI monomer ratio of residual monomer in Table 1 are shown in the upper half of Table 7. 10 < Production of polishing pad > The foamed polyurethane block was heated to about 50 ° C, and cut with a microtome (VGW-125, manufactured by AMITEC) to a thickness of 2 legs, to obtain a foamed polyurethane sheet. The sheet is cut into a circle with a diameter of 610 calendars, and is made into a grid shape on the 15 surface of the sheet (groove width 2.0 legs, groove depth 0.6 mm, groove 1.5 mm) groove processors, and groove processors with concentric circles (groove width 0.3 coffee, φ groove depth 0.4 legs, groove pitch 丨 · 5 mm). Yu Shiyou A commercially available cushioning material for a polishing pad is adhered to the grooved foamed polyurethane sheet with a double-sided tape, and a polishing pad sample is completed. 20 Using the obtained polishing pad, the polishing rate is measured and the evaluation results are aggregated. , Shown in Table 7. 92 1222390 发明, description of the invention. [Table 7]

Example 7-1 Example 7-2 Example 7-3 Example 7-4 Example 7-5 Comparative Example 7-1 Comparative Example 7-2 Comparative Example 7-3 Comparative Example 7-4 Comparative Example 7-5 Comparative Example 7-6 HMDI (wt%) 8.1 12.5 1.4 0.5 8.1 7.6 15.4 13.0 3.2 1.8 8.1 TDI (wt%) 3.7 6.4 0.9 0.8 3.7 13.3 6.2 3.5 0.9 4.1 3.7 HMDI + TDI 11.8 18.9 2.3 1.3 11.8 20.7 21.6 16.5 4.1 5.9 11.8 HMDI / TDI 2.2 2.0 1.6 0.6 2.2 0.6 2.5 3.7 3.6 0.4 2.2 Addition amount of surfactant (wt%) 2.3 2.3 2.3 2.3 4.5 2.3 2.3 2.3 2.3 2.3 7.3 Evaluation result Use time 3'40 ”3,30 ”3,30” 2,40 ”3,45” 2,40 ”4,00” $ 5 '25, 2'10 ”4Ί0” Moldability evaluation 〇〇〇〇〇〇〇XXX 〇 Grinding speed 2700 2450 2850 2900 2300 1400 1500 2500 2800 — 1650 Evaluation of grinding characteristics 〇〇〇〇〇XX 〇〇- X

It is clear from Table 7 that the other polishing pad of the present invention shows good results in any evaluation. In contrast, Comparative Examples 7-1, 7-2, where the residual ratio of isocyanate monomer exceeds 20% by weight, cannot meet the grinding characteristics, while the residual ratio of isocyanate 5 acid vinegar monomer is below 20% by weight but the HMDI / TDI weight of residual monomer Comparative Examples 7-3 and 7-4 whose ratio exceeds 3.2 hardened slowly and could not meet the requirements of formability. Comparative Example 7-5, in which the HMDI / TDI weight ratio was less than 0.5, was too short to use for molding. In addition, Comparative Examples 7 to 6 in which the polysiloxane-based surfactant was added in an amount exceeding 5 wt%, although the isocyanate monomer residual ratio and 10 HMDI / TDI weight ratio were all within the scope of the present invention, they could not meet the requirements of the polishing characteristics. [Example 8] (Example 8-1) Put a toluene diisocyanate (2,4-is / 2,6-is = 80/2 15 mixture) in a container, 14790 parts by weight, 4,4, -Dicyclohexyl methyl roast two different gas 93 1222390 发明, description of the invention

3,930 parts by weight, 25,150 parts by weight of polytetramethylene glycol and 2,756 parts by weight of diethylene glycol with a number average molecular weight of 1,006 and a molecular weight distribution of 17, and heated at 80 C for 120 minutes to obtain an isocyanate equivalent of 2.1 〇meq / g of prepolymer. Into this prepolymer are mixed Aspenser 55IDE (transliteration: small seven hollows, a copolymer of vinylidene chloride and acrylonitrile; a hollow body; ) Co., Ltd.) 148 parts by weight, and vacuum degassed. First, the prepolymer mixture was adjusted to 800 ° C, and while stirring, 12016 parts of 4,4, -methylene-bis (o-aniline) melted in advance at 120X: was added. After stirring for about 丨 minutes, the mixed solution was injected into a disc-shaped open mold, and was subjected to secondary hardening at 110 ° C for 6 hours by a heating furnace to form a foamed polyurethane block. The Gpc measurement of the molecular weight of a polyhydric alcohol such as polytetramethylene glycol is performed by the above-mentioned measurement method using a GPC device (manufactured by Shimadzu Corporation) LC_10A.

15 The analysis of the polyol component used to form the polyurethane polishing pad is performed after the polyurethane is decomposed. The analysis sequence is as follows. a) Collect the polyurethane abrasive pad sample in a PTFE container, add 7.0m bite and 0.5m bite, and then put the entire container into a stainless steel pressure cooker and heat it at 160 ° C for 8 hours to decompose. . 20 b) Extract the decomposed solution with digas methylbenzene / 2N_HC1 (mixing ratio in). The polyol will be extracted into the dichloromethane layer, which can be separated and taken out. C) The solvent was distilled off from the digas methane layer, and the obtained polyol was subjected to GPC measurement by the above method. The identification of the polyol component can be performed by a known analysis method. For example, the method of measuring 94 1222390, the description of the invention, the method of determining the IR spectrum of the polyol obtained by the above decomposition, and the method of analyzing by GC-MS method. In addition, analysis can be performed by thermal decomposition GC-MS method of a polyurethane polishing pad. Subsequently, the foamed polyurethane block was heated to about 50 ° C., and cut into a thickness of 27 mm with a 5 microtome (VGW-125 manufactured by AMITEC) to obtain a polishing layer. A strip with a width of 5 legs was cut out from this thin layer to measure the elastic modulus. The method for measuring the elastic modulus was measured with a dynamic viscoelasticity measuring device Rheogel-E400 (manufactured by UBM), and a sine wave vibration was applied with a tensile test jig, and the measurement was performed at a frequency of 1 Hz. The temperature-dependent mode was used to measure a temperature between 20 ° C and 80 ° C, and the storage elastic modulus at 20 ° C, 40 ° C, and 60 ° C was used as the elastic modulus at each temperature. The elastic modulus of the obtained abrasive layer at 20 ° C, 40 ° C, and 60 ° C was 404Mpa, 299Mpa, and 190Mpa, respectively. 15 Attach a double-sided tape (double tack tape # 5673FW, manufactured by Sekisui Chemical Industry Co., Ltd.) to the obtained polishing layer to complete the polishing pad. The polishing pad thus obtained was evaluated for polishing characteristics using a CMP polishing apparatus (SPP-600S manufactured by Okamoto Machine Tool Co., Ltd.) and a silicon wafer having an oxide film deposited thereon. At this time, at a flow rate of 150 g / min, a silicon dioxide slurry (RD97001 manufactured by Fujimi Incorporated) adjusted as ρΗΐι was used as a polishing liquid, and a grinding load of 350 g / cm 2 was applied while the polishing pad was rotated at 35 rpm. Wafer rotation was 33 rpm for polishing experiments. In terms of polishing characteristics, the average polishing rate and the in-plane uniformity were evaluated. The average polishing rate at the time of polishing 0.5 μηι 95 1222390 玖 was calculated using a 1 μm thermal oxide film deposited on a 6 u-inch silicon wafer. At this time, the in-plane film thickness of the wafer was measured at 28 points, and the in-plane uniformity was calculated by the following formula. The smaller the in-plane uniformity, the better the uniformity. In-plane average sentence 1 ± (/ 〇) — {(Maximum film thickness—Minimum film thickness) / (2x average film thickness 5)} xlOO 'The average grinding speed of the obtained grinding mill is $ 135qA / min, while the in-plane sentence is uniform Is 7%. (Example 8-2) A polishing layer and a polishing pad were prepared in the same manner as in Example 8-1 except that polymethyltetramethylene glycol having a number average molecular weight of 990 and a molecular weight distribution of 15 was 2475 weight parts. . Table 8 shows the elastic modulus, average polishing rate, and in-plane uniformity measured from the obtained polishing layer and polishing pad. (Comparative Example 8-1) 15 Except that 25450 parts by weight of polytetramethylene glycol having a number average molecular weight of 1018 and a molecular weight distribution of 2.0 was used, grinding was performed in the same manner as in Example 8-1. Layer and grind. Table 8 shows the elastic modulus, average polishing rate, and in-plane uniformity measured from the obtained polishing layer and polishing pad. 2〇, ___— [Table 8] Modulus of elasticity (MPa) Average grinding speed Uniformity in plane 20 ° C 40 ° C 60 ° C (A / min) (%) Example 8-1 404 299 190 1350 7 Implementation Example 8-2 390 308 205 1450 5 Comparative Example 8-1 410 271 160 1100 11 From the results shown above, it can be seen that the average polishing speed of the other polishing pad of the present invention is large, the in-plane uniformity is also good, and Perform stable flattening plus 96 1222390 玖, invention description. This can also be known from the elastic modulus of each temperature, and the temperature dependence of the elastic modulus is small. Therefore, it is possible to control the change in the hardness of the grinding (elastic modulus) caused by the frictional heat between the polishing pad and the workpiece during grinding to a minimum. Within range. < [II] Polishing pad > 5 In another polishing pad of the present invention, the high-molecular material used as the matrix material of the polishing layer is not particularly limited. The polymer material can be exemplified by polyurethane, polyethylene, polyamide, acrylic resin, and alkanes resin. As described in "J", it is desirable to have a characteristic that a desired physical property can be obtained by various changes in abrasion resistance and raw material composition. Among them, polyurethane is most preferable. In the following, a description will be given by using polyurethane as the representative polymer material. The polyurethane is composed of an organic polyisocyanate, a polyol compound, and a chain extender. As the organic polyisocyanate, compounds known in the polyurethane field can be used without particular limitation. The organic polyisocyanate can be exemplified by the following types, such as: 2,4 · toluene diisocyanate, 2,6_toluene diisocyanate, diphenylmethane diisocyanate, 2,4'-diisocyanate Diphenylmethane, 4, diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene Aromatic diisocyanates such as diisocyanate 20, ethyl diisocyanate, aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, and 1,6-hexamethylene diisocyanate Isocyanates, 1,4-cyclohexane diisocyanate, 4,4, -dicyclohexyl methane diisocyanate, isophorone diisocyanate, hydrogenated m-xylylene diisocyanate, norfosyl diisocyanate, etc. Diisocyanates and the like. Its 97 1222390 玖, invention description, etc. can be used singly or in combination of two or more. As the organic polyisocyanate, in addition to the above-mentioned diisocyanate compound, a polyfunctional polyisocyanate compound having three or more functions may be used. Multifunctional isocyanate compounds are commercially available with a series of diisocyanate additions such as Desmodur-N (Desmodur-N, manufactured by Bayer Co., Ltd.) or the trade name Duranate (made by Asahi Kasei Corporation).物 olecular compounds. The polyol compound is exemplified by those generally used as a polyol compound in the technical field of polyurethane. For example, the following high molecular weight polyols can be used as the polyol compound. 10 ①Polyether polyols Polyether polyols can be exemplified by the following types, such as: one kind of polyol such as ethylene glycol, diethylene glycol, propylene glycol, propylene glycol, glycerin, trimethylolpropane Or two or more kinds of polyoxypropylene polyols obtained by adding propylene oxide; polyoxyethylene polyols obtained by adding ethylene oxide; polyhydric alcohols obtained by adding butane 15 alkylene oxide, styrene oxide, etc. And polytetramethylene ether glycols obtained by adding tetrahydrofuran to the aforementioned polyol by ring-opening polymerization. A copolymer obtained by mixing two or more kinds of the above-mentioned cyclic ethers may be used. ②Polyester polyols and polyester polyols can be exemplified by the following types, such as ethylene glycol, i, 2-20 propylene glycol, 1,3-propanediol, butanediol, ispentyl glycol, hexanediol, 1, Glycols such as 4-cyclohexanedimethanol, neopentyl glycol, 3-methylpentanediol, diethylene glycol, triethylene glycol, 1,4-bis (2-hydroxyethoxy) benzene; glycerol, One or more of trihydroxymethylpropane, pentaerythritol, or other low molecular weight polyols, and glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, tetra 98 hydrazone, invention description, ugly acid, Isophthalic acid, dimer acid, hydrogenated dimer acid or other low-molecular dimer acid or oligomer acid i or two or more polycondensates, propiolide, caprolactone, valerolactone, etc. Polyols such as ring-opening polymers of cyclic esters. As the aforementioned poly (vinyl alcohol) 7G alcohol, polybutylene adipate and polycaprolactone polyol are taken as representative examples. ③ Polycarbonate polyols Polycarbonate polyols can be exemplified by the following, such as: polyester diol and alkylene carbonate reactants, such as polyester polycarbonate polyols of polycaprolactone; The reaction of the ethyl ester with the polyhydric alcohol causes the obtained reaction mixture to react with a polyacrylic acid carbonate polyol having 10 units of monoacid; and the one obtained by the transesterification reaction of a polyacrylic compound with an aryl carbonate. ④ Acrylic polyols can be used in acrylic copolymers. Monoethylenically unsaturated monomers having a hydroxyl group in a molecule such as a comonomer are propylene 15 acid polyols having two or more hydroxyl groups in one molecule, such as β-hydroxyethyl acrylic acid. Hydroxyalkyl esters of acrylic acid such as β-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, β-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, β-hydroxypentyl acrylate or the same A hydroxyalkyl ester of methacrylic acid, and further an acrylic monoester of a polyhydric alcohol such as glycerin, trimethylolpropane, or the same methacrylic monoester, N-hydroxypropylpropene 20 amine or NH Methylmethacrylamide and the like. As the acrylic polyol, a telechelic acrylic polyol can also be used. The telechelic acrylic polyol is a hydroxy-containing acrylic acid obtained by polymerizing an unsaturated monomer containing a (meth) acrylate in the presence of an alcohol compound by using an organic peroxide-containing initiator in the presence of an organic sulfonic acid compound. 99. Description of the invention = compound. The aforementioned alcohol compounds are preferably aliphatic or alicyclic enzymes such as methanol and ethanol. If a monofunctional alcohol is used as the alcohol compound, the active fluorene group-containing acrylic polymer prepared is substantially bifunctional. As an alcohol compound, an alcohol is an active hydrogen-containing propionate-based polymer that is substantially four-functional. ⑤ Other polyols can also be used: resin polyol, epoxy polyol, polybutadiene alcohol, polyisoprene polyol, polyester · polyether polyol, acrylonitrile or styrene, etc. A polymer polyol having a vinyl group, a urea-dispersed polyol, a carbonate polyol, and the like are added and dispersed in the polymer as the polyol of the present invention. In addition, a polyol compound in which these polyol compounds are condensed with p-aminobenzoic acid and having a halogenated active gas group as an aromatic amine group can also be used. The number-average molecular weight of these high-molecular-weight polyols is not particularly limited, but from the viewpoint of the elastic properties of the polyurethane to be obtained, it is preferably in the range of about 500 to 2000. If the number average molecular weight of the high-molecular-weight polyol is less than 500, the polyurethane produced therefrom does not have sufficient elastic characteristics, and forms a brittle polymer, which is easy to wear, so from the standpoint of grinding life Not ideal. On the other hand, if the number average molecular weight exceeds 2000, the polishing layer based on the obtained polyurethane as a substrate becomes soft, and the flatness sufficiently required can not be obtained. In addition to the above-mentioned high-molecular-weight polyol, the polyol compound may be used in combination with a low-molecular-weight polyol such as a polyester polyol. These polyol compounds may be used singly or in combination of two or more kinds. In addition, the ratio of high-molecular-weight polyols to low-molecular-weight polyols in polyol compounds is not specifically limited to 1222390 发明, the description of the invention, and is a characteristic required for the polishing layer of a polishing pad with respect to a polyurethane produced therefrom Decide. In another polishing pad of the present invention, it is preferable that the polyol compound contains a water-soluble polymer polyol, and the polyurethane is adjusted to the aforementioned swelling degree. 5 In addition, the definition of "water-soluble" in "water-soluble polymer polyol" is that polymer polyol has the property that it can be completely mixed with water of the same capacity. The water-soluble high-molecular polyol can be exemplified by polyethylene glycol among the polymer polyols listed above. Examples of water-soluble polymer polyols other than those listed above include monobasic acids having ionic groups such as dibasic acids having a sulfonic acid (salt) group (for example, 5- (tetra-n-butyl scale) sulfonic isophthalic acid 10). As an example, a polyester polyol obtained by copolymerization of a polymer is used. The proportion of the water-soluble polymer polyol in the full polyol compound is not particularly limited, but it is preferably within a range of about 1% to 70% by weight. If the proportion of water-soluble polymers decreases, the degree of swelling of the obtained polyurethane becomes smaller, and the swelling degree in the wet environment under the supply of the grinding liquid cannot be sufficiently increased, and the surface of the grinding layer cannot be sufficiently softened, and there is formation. Because of the risk of scratches, the proportion of the water-soluble polymer polyol is preferably 1% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% by weight or more. Conversely, if the proportion of the water-soluble polymer polyol is too large, the swelling degree of the polyurethane becomes large. In a humid environment under the supply of the grinding liquid 20, not only the surface but also the inside are wet, which causes the entire polishing layer to soften, and there is The flatness may not be improved. Therefore, the proportion of the water-soluble polymer polyol is preferably 70% by weight or less, more preferably 65% by weight or less, and particularly 60% by weight or less. In addition, in another polishing pad of the present invention, in consideration of 101 1222390, which is obtained by the aforementioned method, and the hydrolytic resistance of the polyurethane, it is preferable to use an ether polyol as the polyol compound. Furthermore, in order to increase the wettability of the obtained polyurethane to water to the extent of having an optimal contact angle, the polyol component preferably contains an ether-based water-soluble diol. The ether-based water-soluble diol refers to a diol having an ether bond 5 in the molecule and having the property of being completely mixed with water of the same capacity. As the ether-based water-soluble diol, the above-exemplified polyhydric alcohol and even polyethylene glycol, diethylene glycol, and triethylene glycol in the polyhydric alcohol compound are preferably used. These water-soluble diols may contain only one kind, or two or more kinds. It is also possible to use three or more functional polyfunctional components together. The proportion of the ether-based water-soluble diol in the 100% alcohol compound is not particularly limited, but it is preferably in the range of about 1% to 85% by weight. If the proportion of water-soluble diol is reduced, the wettability of polyurethane is insufficient (the contact angle with water becomes larger), the polishing speed is low, and uniform polishing cannot be performed, which may cause scratches. The proportion of water-soluble diol is preferably more than 5% by weight, more preferably 15% by weight or more, and particularly preferably 8% by weight or more. Conversely, if the proportion of the water-soluble diol of the test system is increased, the wettability and wettability of the polyurethane (the contact angle with water becomes smaller), and the grinding speed may be unstable. The proportion of alcohol is preferably 85% by weight or less, more preferably 80% by weight or less, and particularly preferably %% by weight or less. 20 The qichang agent is an organic compound having at least two active hydrogen groups. Examples of the active hydrogen group include a peptidyl group, a first- or second-order amine group, and a thiol group (SH). The chain extender is a compound having a molecular weight of about 500 or less. Specifically, the above-mentioned low-molecular-weight polyols may be exemplified by the following, such as: 4,4, methylenebis (o-aniline), 2,6, dichloro-p-phenylenediamine, ο, methylene 102 1222390发明 、 Analytical bis (2,3-digas aniline), dicyclohexyl methyl-M, -diamine and other aromatic or aliphatic diamines, 丨, 4-bishydroxyethoxybenzene (Qiu Ming (transliteration: S >) H (manufactured by IHARA Chemical Co., Ltd.)), m-xylene glycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and other aromatic diols. 5 The ratio of the organic polyisocyanate, the polyol compound, and the chain extender in the present invention can be variously changed depending on the respective molecular weights or the desired physical properties of the polyurethane (grinding layer) made from them. In order to obtain a polishing pad having desired polishing characteristics, the organic polyisocyanate 10 vinegar isocyanate is equivalent to the number of functional groups (total of active hydrogen groups such as radicals and amine groups) of the polyol compound and the chain extender. The base number should be in the range of 0.9HW, and more preferably in the range of 099 ~ uo. The ratio of the high-molecular weight component to the low-molecular weight component in the polyol compound can be determined by the characteristics required of the microfoamed polyurethane produced therefrom. The manufacturing method of the polyurethane and the polishing pad is not particularly limited, but the method described above can be used. In addition, in another polishing pad of the present invention, the addition amount of the polysiloxane surfactant is preferably 0.1% to 5% by weight based on the polyurethane raw material (the total amount of the i-th component and the second component). If it is less than 0.01% by weight, a fine foamed body cannot be obtained. From this viewpoint, the addition amount of the polysiloxane-based surfactant is preferably i% by weight or more. On the other hand, if it exceeds 5% by weight, the number of bubbles in the micro-foamed polyurethane is increased, and it is difficult to obtain a micro-foamed polyurethane having a high hardness. In addition, the strength of the polishing layer is reduced, and the planarization characteristics are reduced during polishing. From this viewpoint, the addition amount of the polylithic oxygen-based surfactant is preferably 5 wt% or less. 103 1222390 (ii) Description of the invention Examples The invention will be described in more detail by way of examples below, but the scope of the invention is not limited by these examples. [Example 9] 5 Reference Example 9-1 (Production of polyurethane block) Put diisocyanate toluene (2,4-body / 2,6-body = 80/20 in a container) Mixture: hereinafter referred to as TDI) 1,566 parts by weight, 4,4'-dicyclohexylmethane diisocyanate (hereinafter referred to as HMDI) 786 parts by weight, and a number average molecular weight of 844 polytetramethylene glycol (hereinafter referred to as PTMG) 790 1310 parts by weight of polyethylene glycol (hereinafter referred to as PEG) with a number average molecular weight of 600, 331 parts by weight of diethylene glycol (hereinafter referred to as DEG), and heating and stirring at 80 ° C. for 150 minutes to obtain an isocyanate-terminated prepolymer . After the prepolymer mixture was degassed in a vacuum, the temperature was adjusted to 80 ° C, and then the mixture was mixed for 15 minutes and added in advance at 120 ° C. (: Melted 4,4, -methylene-bis (o-chloroaniline) (hereinafter referred to as MBOCA) 1520 parts by weight. After stirring for about 1 minute, the mixed solution is poured into a disc-shaped open mold, and the heating furnace is used to 110 After secondary hardening at 6 ° C for 6 hours, a non-foamed polyurethane block was obtained. (Measurement of swelling degree) 20 The obtained polyurethane block was used to form a block with a thickness of 2G imnx20 mm at a thickness of 2 When the test piece was immersed in the pit's pHU hydroxide solution for 24 J, the swelling degree was calculated by the following formula, and the swelling degree was 7.5%.

Lake expansion (%) = π (weight of original weight after 24 hours) / (original weight)] xlOO 104 1222390 发明, description of the invention

Example 9-1—A (Production of microfoamed polyurethane block) An isocyanate-terminated prepolymer was prepared in the same manner as in Reference Example 9-1. Thereafter, a polysiloxane surfactant (manufactured by Toray Road 5 Corning Shixijiao Co., Ltd., sh-192: hereinafter abbreviated as .192) was mixed with 20 parts by weight of the prepolymer, and the temperature was adjusted to 8 (rc. While stirring, add 1520 parts by weight of MBOCA that was previously melted at 120 ° C. After stirring for about i minutes, the mixture is poured into a disc-shaped open mold and heated at 1100c for 6 hours. -When the human is hardened, a micro-foamed polyurethane block (pore diameter 4 is called m 10) is made. The density of the obtained micro-foamed polyurethane is 0.75 g / cm 3. In addition, the density measurement system is According to JIS K 7222 (Measurement of apparent density of foamed plastic and rubber). (Measurement of storage elastic modulus) Next, the micro-foamed polyurethane block is heated to about 5 (rc, 15 and A slicer (made by AMITEC Corporation, VGW_125) was cut to a thickness of 1.27 to obtain a polished layer. A strip with a width of 5 mm was cut from the thin layer, and the storage elastic modulus was determined to be 325 MPa. Method for measuring the elastic modulus A dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) was used to apply a 20% sine using a tensile tester. Vibrate and measure at a frequency of 1 Hz. Measure from 20 ° C to 80 ° C in a temperature-dependent mode, and use the storage elastic modulus at 40 ° C as the elastic modulus. (Production of polishing pads) The obtained polishing layer Attach a double-sided tape (manufactured by Sekisui Chemical Industry Co., Ltd., 105 1222390 玖, double tack tape # 5782), and finish polishing. The polishing characteristics of the obtained polishing pad were evaluated using a CMP polishing apparatus (manufactured by Okamoto Machine Tool Co., Ltd., SPP- 600S). Grinding conditions are such that a silicon dioxide slurry (Fujimi 5 Incorporated, RD97001) adjusted to pH 11 is injected as a polishing liquid at a flow rate of 150 g / min, while the grinding load is 350 g / cm 2 3. Polishing (flatness) with polishing pad rotations of 35 rpm and wafer rotations of 33 rpm. Flatness was evaluated by depositing a 0.5 μm thermal oxygen 10 film on a 6-inch silicon wafer and performing L / S (wire and Gap) = 25μηι / 5μιη and L / S = 5μιη / 25μηι patterned, and then a 1μηι oxide film (TE0S) was deposited to make a wafer with a pattern with an initial drop of 0.5μπι. The wafer was ground as described above Conditional advance During polishing, the total drop is 2000A or less, and the bottom reduction of the 25μm gap is measured and evaluated. The flatness 15 of the obtained polishing pad is measured at 75nm. The smaller the flatness value, the better. (Scratch) Evaluation of scratches For those who use a ιμηι thermal oxide film deposited on a 6-inch silicon wafer and grind it under the above conditions to a thermal oxide film of 0.5μηι, the wafer is washed and dried, and then KLA (made by KLA Tencor Corporation) is used. , 20 KLA2112) was evaluated by measuring micro-scratch. This evaluation measured 10 scratches on 1 wafer. (Polishing speed) The evaluation of the polishing speed is performed by using a 1-μm thermal oxide film deposited on a 6-inch silicon wafer and polishing it under the above conditions until the thermal oxide film is 0.5 μm, 106 1222390 玖, description of the invention

The grinding speed is then determined from the grinding time at that time. The polishing rate of the obtained polishing pad was 115 nm / min. The larger the grinding speed, the better. Example 9-1—B A non-foamed polyurethane block obtained from Reference Example 9-1 was prepared in the same manner as in Example 9-1 1-A, and its polishing characteristics were evaluated. The results are shown in Table 9. In addition, when the density and storage elastic modulus of this non-foamed polyurethane were measured in the same manner as in Example 9-1A, the density was 1.18 g / cm 3 and the storage elastic modulus of the abrasive layer was measured. It was 970 MPa. Reference Example 9-2 10 (Production of polyurethane block) Put TDI 1566 parts by weight, HMDI 786 parts by weight, PTMG 1580 parts by weight average molecular weight 844, PEG 749 by number average molecular weight 600 Part by weight, DEG 331 parts by weight, and heating and stirring at 80 ° C. for 120 minutes to obtain an isocyanate-terminated prepolymer. After degassing the prepolymer 15 mixture in a vacuum, first adjust the temperature to 80 ° C and then stir while adding 1520 parts by weight of MBOCA which was previously melted at 120 ° C. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C. for 6 hours by a heating furnace to obtain a non-foamed polyurethane block. The degree of swelling of the obtained non-foamed polyurethane agglomerates was measured in the same manner as in Reference Example 9-1, and was found to be 2.8%.

Example 9-2 —A (Production and Evaluation of Microfoam Polyurethane Blocks) An isocyanate-terminated prepolymer was prepared in the same manner as in Reference Example 9-2. Thereafter, 210 parts by weight of SH-192 was added to the prepolymer and mixed. 107 1222390 玖, description of the invention

Close and adjust the temperature to 80 ° C. While stirring, 1520 parts by weight of MBOCA, which was previously melted at 120 ° C, was added. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C. for 6 hours by a heating furnace to form a micro-foamed polyurethane block (pore size 40 μπι). . When the density and storage elastic modulus of the microfoamed polyurethane obtained in 5 were measured in the same manner as in Example 9-1—A, the density was measured to be 0.74 g / cm 3, and the storage elastic modulus of the abrasive layer was The number is 310 MPa. A polishing pad was produced in the same manner as in Example 9-1 -A, and the polishing characteristics were evaluated. The results are shown in Table 9. Example 9 — 2 —B 10 A polishing pad was prepared from the non-foamed polyurethane block obtained in Reference Example 9-12 in the same manner as in Example 9-1 —A, and the polishing characteristics were evaluated. The results are shown in Table 9. In addition, when the density and storage elastic modulus of this non-foamed polyurethane were measured in the same manner as in Example 9-1—A, the density was measured to be 1.17 g / cm 3 and the storage elastic modulus of the abrasive layer It is 929 MPa.

15 Reference Example 9-3 (Production of polyurethane block) Put a polyether prepolymer (AdipreneL-325; manufactured by Unilo Corporation; isocyanate group concentration 2.22meq / g) in a container 500 weight And vacuum degassed. At this time, while stirring, 145 parts by weight of MBOCA melted in advance at 120 20 ° C was added. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C for 6 hours by a heating furnace to obtain a non-foamed polyurethane block. When the degree of swelling of the obtained non-foamed polyurethane block was measured in the same manner as in Reference Example 9-1, it was measured to be 1.8%. 108 1222390 发明, description of the invention

Comparative Example 9-1A (Production and Evaluation of Micro Hollow Polyurethane Blocks) · A polyether prepolymer (Adiprene. L-325; manufactured by Unilo Corporation; isocyanate group) was mixed in a container. Concentration 2.22meq / g) 500 parts by weight with Aspan 5se 551DE (transliteration: only eight ^ seven less, the gasification of the copolymer of vinylene and acrylonitrile is a tiny hollow body; (B) 13 parts by weight of the company) and vacuum degassing. At this time, 145 parts by weight of MBOCA melted in advance at 120 ° C was added while stirring. After stirring for about 1 minute, the mixed solution is poured into a disc-shaped open mold and subjected to secondary hardening at 10 U0 ° C for 6 hours by a heating furnace to obtain a polyurethane hollow block containing tiny hollow bodies ( Pore diameter 40 μm). As for the polyurethane containing fine hollow bodies, when the density and storage elasticity were measured in the same manner as in Example 9-1A, the density was measured as 0.75 g / Cm 3 and the elastic modulus of the abrasive layer was 268 MPa. Then, a polishing pad was produced in the same manner as in Example 9-11, and the polishing characteristics were evaluated. 15 The results are not shown in Table 9. Comparative Example 9 — 1 — B _ Non-fat produced by Reference Example 9-3 An agglomerated polyurethane block was prepared in the same manner as in Example 9-1—A, and the polishing characteristics were evaluated. Results are shown in 纟 9. In addition, when the density and storage elastic modulus of the non-foamed polyurethane were measured in the same manner as in Example 9-1-A of Example 20, the density was measured at 1.19 g / Cm 3 and the storage elasticity of the abrasive layer was measured. The modulus is 75 MPa. Reference Example 9-4 (Production of polyurethane block) Put TDI 1566 parts by weight, HMDI 786 parts by weight, 109 1222390 玖 into the container, description of the invention

318 parts by weight of PTMG having a number average molecular weight of 844, 2623 parts by weight of PEG having a number average molecular weight of 1,000, and 318 parts by weight of DEG, and heated and stirred at 80 ° C for 120 minutes to obtain an isocyanate-terminated prepolymer. After the prepolymer mixture was degassed in a vacuum, the temperature was adjusted to 80 ° C, and then while stirring, 520 parts of MBOCA melted at 120 ° C in advance were added. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold, and subjected to secondary hardening at 110 ° C. for 6 hours by a heating furnace to obtain a non-foamed polyurethane block. The degree of swelling of the obtained non-foamed polyurethane agglomerates was measured in the same manner as in Reference Example 1-1, and was found to be 17.4%.

10 Comparative Example 9-2 —A (Production and Evaluation of Microfoam Polyurethane Blocks)

An isocyanate-terminated prepolymer was prepared in the same manner as in Reference Example 9-4. Thereafter, 190 parts by weight of SH-192 was mixed in the prepolymer, and the temperature was adjusted to 80 ° C. While stirring, 1520 parts by weight of MBOCA which had been previously melted at 120 15 ° C was added. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold and subjected to secondary hardening at 110 ° C for 6 hours by a heating furnace to prepare a micro-foamed polyurethane block (pore diameter 40 μπο). When the density and storage elastic modulus of the obtained micro-foamed polyurethane were measured in the same manner as in Example 9-1—A, the density was measured to be 0.84 g / cm 3, and the storage elastic modulus of the abrasive layer 20 was The number was 271 MPa. A polishing pad was produced and evaluated for polishing characteristics in the same manner as in Example 9-1 —A. The results are shown in Table 9. Comparative Example 9 — 2 — B None obtained from Reference Example 9-4 A foamed polyurethane block was made into a polishing pad in the same manner as in Example 9-1—A, and the polishing characteristics were evaluated. 110 1222390 玖, description of the invention. The results were not as good as 纟 9. When the polyurethane and the elastic modulus of storage were measured in the same manner as in Example 9-1-A, the rush degree was 1.18 g / cm 3, and the storage elastic modulus of the abrasive layer was 754 MPa. 9] Swelling degree (%) Density (g / cm3) Storage modulus of elasticity (MPa) Flatness (nm) Scratches (a) Grinding speed (nm / min) Λ Iya 1J 9-1 A Microfoaming 7.5 0.75 325 75 10 115 B None ~ Example 9-2 1 A Microfoaming 2.8 1.18 970 40 58 35 0.74 1.17 310 Q2Q 75 λ ς 14 110 B No foaming Comparative Example 9-1 A Micro hollow body 1.8 Bu 0.75 1.19 268 ΊKO〇 100 cc 50 90 40 115 B No foaming Comparative Example 9-2 Bu A Microfoam ~ 17.4 0.84 / J \ J 271 J 120 3 80 8 35 110 B Non-foaming 1.18 754 95 15 45 It is clear from Table 9 that the polishing pad prepared by the present invention can coexist with the two effects of improving flatness and reducing scratches. Those who form microfoam also meet the polishing speed. [Example 10] < Evaluation method > 10 (Measurement of contact angle) Foamed polyurethane was placed on two pieces of 0.2-foot-thick tetrafluoroethylene resin tape (Naflon tape TOMBO manufactured by NICHIAS Corporation). 9001), and then it was sandwiched between two iron plates with a thickness of 1 leg and formed by a hot press to a thickness of about 100 μm. The temperature was 215 and the pressure was 5 Mpa. Lee 15 used the film A contact angle meter CA-X made by Kyowa Interface Science Co., Ltd. was used to measure the contact angle with water by the droplet method. Measurement temperature The value is 25. (: Humidity is 60%, and the measured value after dropping for 1 minute is used. (Polishing characteristics) The polishing characteristics of the polishing pads were evaluated using a CMP polishing device SPP-111 1222390 玖, Invention Description 600S (manufactured by Okamoto Work Machinery Co., Ltd.) )get on. Grinding conditions were as follows: at a flow rate of 150 g / min, SiO 2 RD-97001 (manufactured by Fujimi Incorporated), which has been adjusted to pH 11 as a polishing liquid, was injected, and the grinding load was 350 g / cm 2. The rotation was performed at 35 rpm and the wafer was rotated at 5 rpm and 33 rpm. The polishing characteristics were evaluated for in-plane uniformity, average polishing rate, polishing rate stability, and scratches shown below. (In-Plane Uniformity) A 6-inch silicon wafer with a thermal oxide film of 1 μm was stacked and polished under the above-mentioned polishing conditions for 5 minutes. Then, the in-plane film thickness of the wafer was measured at 28 points, 10 and calculated from the following formula. In-plane uniformity. The smaller the evaluation value of the in-plane uniformity, the better the uniformity. In-plane uniformity (%) = {(maximum film thickness-minimum film thickness) / (2 × average film thickness)} x100 (average polishing rate) 15 A thermal oxide film 1 μηι was deposited on a 6-inch silicon wafer, and The polishing was performed for 5 minutes under the above polishing conditions, and the average polishing rate was determined from the reduction amount at that time. The larger the evaluation value of the average polishing rate, the better. (Polishing speed stability) A 6-inch silicon wafer with a thermal oxide film of 1 μηι is used, and the polishing is performed continuously for 5 times and 1 minute under the above-mentioned 20 polishing conditions, and the polishing rate for each time is obtained, and then the following The formula determines the polishing rate stability. The smaller the grinding speed stability, the better. Grinding speed stability (%) = {(maximum grinding speed)-(minimum grinding speed

Degree) / (average polishing rate)} xlOO 112 玖, description of the invention (scratch) The evaluation of scratches is performed by using a 6-inch silicon wafer with a 1 (xm thermal oxide film), and polishing is performed under the above conditions for 5 minutes. After that, the wafer was washed and dried, and then micro scratches were measured by KLA (KLA Tencor, KLA 2112). The smaller the scratch value obtained in the evaluation, the better the polishing layer material. (Example 10— 1) < Production of abrasive layer material > Put xylene diisocyanate (mixture of 2,4-body / 2,6-body = 80/20 in the container: hereinafter referred to as TDI) 1566 parts by weight, 4 , 4,4-Dicyclohexylmethane diisocyanate (hereinafter referred to as HMDI) 786 parts by weight, polytetramethylene glycol (hereinafter referred to as ptmG) having a number average molecular weight of 1006, 1509 parts by weight, and a polyethylene glycol having a number average molecular weight of 1,000 ( 1500 parts by weight (hereinafter referred to as peg), 318 parts by weight of diethylene glycol (hereinafter referred to as DEG), and heated and stirred at 80 ° C. for 120 minutes to obtain an isocyanate-terminated prepolymer. At this time, polysiloxane surfactant SH -192 (manufactured by Toray Dow Corning Silicone) 210 parts by weight, and adjust the temperature to 80 ° C. While vigorously stirring to take in air bubbles, 1520 parts by weight of 4,4'-methylenebis (o-aniline) (hereinafter referred to as MBOCA) melted at 120 ° C was added in advance. Stir for about 1 minute Then, the mixed liquid was poured into a disc-shaped open mold, and was subjected to secondary hardening at 110 ° C. for 6 hours by a heating furnace to obtain a foamed polyurethane block (pore diameter 40 μηι). The density of the acid ester block is 0.85g / cm 3. The density is measured in accordance with JIS K 7222 (measurement of the apparent density of foamed plastics and rubbers 1222390 玖, the description of the invention). When the contact angle with water was measured for polyurethane as follows, it was 85. < Production of polishing pad > 5 The foamed polyurethane of the fine bubbles of the obtained polishing pad constituting material was agglomerated. The material was heated to about 50 ° C, and cut with a slicer (VGW_125, manufactured by AMITEC) to a thickness of 127 legs to obtain a foamed polyurethane sheet. The sheets were cut into circular shapes with a diameter of 610 mm and were respectively Made on a sheet surface with a grid pattern (groove width 2.0 mm, groove depth 0.6 mm, groove pitch 10 · Swellers with 5 swellings and grooves with concentric circles (groove width 0.3 mm, groove ice 0.4 surface, groove pitch 1.5 mm). A double-sided tape (double tack tape # 5782 manufactured by Sekisui Chemical Industry Co., Ltd.) was affixed to each of the foamed polyurethane sheets processed in the groove, and the rubbing sample was completed. The evaluation results of the obtained polishing pads are shown in Table 10. 15 (Example 10-2) Except that the amount used in Example 10-1 was changed to the use of TDI 1566 parts by weight, HMDI 786 parts by weight, ptmG 100,000 parts by weight average molecular weight 1000, and the number average molecular weight by 60% An isocyanate-terminated prepolymer was prepared by using pEG 14.0 parts by weight and DEG 331 parts by weight, and 20 MBOCA was 1500 parts by weight. The rest was prepared in the same manner as in Example 110-1. Carbamate agglomerates (pore size 40 μm). The density of the obtained foamed polyamino acid vinegar cake was 0.78 g / cm 3. When the contact angle of the polyurethane composition was measured in the same manner as in Example 10-1, it was found to be 79 °. 114 1222390 (ii) Description of the invention A polishing pad was produced in the same manner as in Example 10-1 and evaluated for polishing characteristics. The results are shown in Table 10. (Example 10-3)

In a container, 500 parts by weight of a polyether-based prepolymer (AdipreneL-325 manufactured by Uniro 5; isocyanate group concentration of 2.22 meq / g) and 19 parts by weight of SH192 were adjusted, and the temperature was adjusted to 80 ° C. At this time, 145 parts by weight of MBOCA melted in advance at 120 ° C was added while vigorously stirring to take in air bubbles. After stirring for about 1 minute, the mixed solution was poured into a disc-shaped open mold, and was subjected to secondary hardening at 110 ° C. for 6 hours by a heating furnace to obtain a foamed poly (urethane) block (pore size: 35 μm). The density of the foamed polyurethane block was 0.86 g / cm 3. When the contact angle of the polyurethane composition was measured in the same manner as in Example 10-1, it was 90 °. In addition, Adiprene was analyzed by proton NMR

The composition of L-325 shows that, for each part by weight of the polyol component, 15 contains about 0.539 parts by weight of PTMG with a number average molecular weight of 1,000, and about 0.057 parts by weight of DEG. A polishing pad was produced in the same manner as in Example 10-1 and evaluated for polishing characteristics. The results are shown in Table 10. (Comparative Example 10-1) 20 Except that the amount used in Example 10-1 was changed to use TDI 1566 parts by weight, HMDI 786 parts by weight, PTMG 302 parts by weight with a number average molecular weight of 1006, and PEG 2700 parts by weight with a number average molecular weight of 1,000. And 318 parts by weight of DEG to make an isocyanate-terminated prepolymer, and the MBOCA was made to 1520 parts by weight. The rest of the shellfish ij was prepared in the same manner as in Example 10-1. Ester agglomerates (pore size 40 μm). The density of the obtained foamed poly (urethane) agglomerates was 0.85 g / cm 3. When the contact angle of the polyurethane composition was measured in the same manner as in Example 10-1, it was 69 °. 5 A polishing pad was prepared in the same manner as in Example 10-1 and evaluated for polishing characteristics. The results are shown in Table 10. (Comparative Example 10-2)

Except that the amount used in Example 10-1 was changed to use TDI 1566 parts by weight, HMDI 786 parts by weight, and PTMG 10 3622 parts by weight with a number average molecular weight of 1.06 to make an isocyanate-terminated prepolymer, and MBOCA was 2136. Except for the parts by weight, the rest was obtained in the same manner as in Example 10-1 to obtain a foamed polyurethane block (pore size: 40 μm). The density of the obtained foamed polyurethane block was 0.84 g / cm3. When the 15 contact angle of the polyurethane composition was measured in the same manner as in Example 10-1, it was 97 °.

A polishing pad was produced in the same manner as in Example 10-1 and evaluated for polishing characteristics. The results are shown in Table 10. [Table 10] Contact angle (°) In-plane uniformity of groove shape Average polishing rate (nm / min) Polishing speed stability (%) Scratches ~ (quote) Example 10 -1 85 Lattice 8.0 110 7.3 20 Concentric circles 8.0 107 7.5 28 Example 10-2 79 Grid 7.5 120 8.3 15 Concentric circles 7.5 123 8.1 12 Example 10-3 90 Grid 8.0 110 7.3 38 Concentric circles 8.5 113 7.1 35 Comparative Example 10-1 69 Grid 7.0 120 13.3 20 Concentric circles 7.5 110 14.5 12 Comparative example 10-2 97 Grid 11.0 85 11.8 122 Concentric circles 10.5 85 11.8 110 As can be clearly seen from Table 10, a pair of grinding pairs 116 1222390 can be produced by the present invention. A polishing pad with uniform polishing and few scratches, and which can stably maintain the required polishing speed. In addition, it is known that these polishing characteristics are closely related to the contact angle of the polymer material used to form the polishing layer to water due to the different shapes and shapes of the polishing pad surface (the groove processing is different). 5 < [III] Abrasive pad > The constituent material of the independent bubble type buffer layer in the other abrasive pad of the present invention is not limited, and the swelling ratio of water within the range shown in the present invention is sufficient. Specific examples include polyolefins such as polyethylene and polypropylene, polyurethanes, polystyrene, polyester, polyethylene gas, polygasified vinylene, and polysiloxanes. In addition, the average bubble diameter and the number of bubbles per unit area of each foam in the independent bubble buffer layer in the present invention are not particularly limited, and may be appropriately set depending on the characteristics of the buffer layer required for the object to be ground or the grinding conditions. . The method for obtaining the independent bubble foam is not limited, and anyone who can obtain a foam having a swelling ratio of 15 water within the range shown in the present invention can be used. Generally speaking, there are several known methods. For example, after the low molecular gas such as co2 is dissolved in the resin at a predetermined temperature and pressure, the dissolved gas is supersaturated by rapid decompression and heating operations. Physical foaming method for generating bubbles in the resin; a method of mixing a low-boiling organic compound in a polymerizable resin raw material and curing while foaming; kneading a chemical foaming agent in a resin raw material ( Reaction material), a chemical foaming method that decomposes and reacts under a predetermined temperature condition to generate gas such as C02 or N2 to generate bubbles in the resin; and mechanically stirs the molten resin or prepolymer to contain bubbles, It can be solidified by cooling, or forced to seal 117 1222390 借 by polymerization reaction, mechanical foaming method of air bubble introduction, etc., can be used for manufacturing the buffer layer of the polishing pad of the present invention. The non-foaming resin material for constituting the buffer layer is not particularly limited, and examples thereof include a photocurable resin, a thermosetting resin, and a thermoplastic resin. 5 The non-foaming resin material should use resins with low elastic hysteresis and compression characteristics of rubber-like elastomers, such as: butadiene polymer, isoprene polymer, styrene-butadiene Copolymer, styrene_isoprene-styrene block copolymer, styrene-butadiene_styrene block copolymer, styrene-ethylene-butadiene_styrene block copolymer , Acrylonitrile_ 10 butadiene copolymer, polyurethane elastomer, epoxy propane rubber, polyvinyl chloride, silicone rubber, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, amine Ethyl acetate thermoplastic elastomer, fluorine-based thermoplastic elastomer, or a photosensitive resin with a cushioning property used in printing materials. The hardness of the buffer layer constituting material of the present invention should preferably be in the range of 10 to 75, and more preferably in the range of 20 to 65. If the material of the buffer layer is low and the A hardness is less than 10, there will be problems of grinding residue (edge sag) or flatness at the periphery of the wafer. If it is greater than 75, uniformity will be a problem. The compression ratio of the buffer layer constituting material of the present invention is preferably ~ 30. Within the range of 20%, it is more preferable to be in the range of 3.5% to 15%. When the compression ratio of the buffer layer constituent material is less than 1.5%, uniformity may be a problem. When it exceeds 30%, grinding residue (edge sag) or flatness of the wafer peripheral portion may cause problems. The compression recovery rate of the layer constituent material should be 118 1222390 玖, the description of the invention should be more than 70%, and more preferably 80%. When the compression recovery rate of the buffer layer constituent material is less than 70%, the stability of the polishing rate will cause problems. The thickness of the polishing layer constituting the polishing pad of the present invention is not particularly limited, and is generally in the range of 0.8 to 2 legs, and the thickness of the buffer layer is preferably in the range of 0.5 to 5 legs. In order to improve the thickness accuracy of the buffer layer in the present invention, it is suitable to perform a polishing process. When the buffer layer and the polishing layer in the present invention are laminated, the surface of the buffer layer may be coated with an adhesive layer and then laminated, or may be laminated with a double-sided tape. Also, if the material constituting the buffer layer is one that can exhibit adhesiveness when heated or irradiated with light, the buffer layer can also be directly laminated on the polishing layer and adhered by heating or light irradiation without additional use. Then agent. When the polishing pad of the present invention is adhered to the polishing table with a buffer layer, the adhesive layer may be coated on the surface of the buffer layer and then adhered, or the double-sided tape 15 may be used for adhesion. In addition, as in the case of laminating with the polishing layer described above, if the material constituting the buffer layer is one that can exhibit adhesiveness when heated or irradiated with light, the buffer layer can also be directly bonded to the polishing platform without additional use. Then agent. When double-sided tape is used to attach the buffer layer, in order to improve the adhesion, it is suitable to perform a surface treatment such as corona discharge treatment on the surface of the buffer layer. In the polishing pad of the present invention, the material constituting the polishing layer is not limited, and any known material for constituting the polishing layer can be used. Specifically, for example, polyurethane, polyester resin, polyether resin, acrylic resin, ABS resin, polycarbonate resin, blended mixtures thereof, photosensitive resin, and the like. These 119 1222390 发明, description of the invention The resin may be a foamed body or a non-foamed resin. The resin constituting the polishing layer is preferably one having a hardness higher than that of the buffer layer and a low compression ratio. Among the above-mentioned polishing layer constituent resins, the use of a polyurethane resin is preferable in terms of excellent polishing characteristics, and it is particularly preferable to use a polyurethane resin foam of the above-mentioned closed cell type 5. The method for producing a closed-cell polyurethane resin foam and a polishing pad is as described above. EXAMPLES The present invention will be described in more detail below through examples, but the scope of implementation of the present invention is not limited to these examples. [Example 11] < Evaluation method > (Swelling rate to water) A sample of a buffer layer constituting material of 1.5 CII1 × 5.0 cm was dried at 5 (rc, 15 24 hr, and placed in a dry state). After the container was left to cool, the weight of the sample was measured with a precision balance. Next, the sample was immersed in distilled water, immersed at 20 ° C and left for 24 hours, and then the sample was removed and the surface was wiped off. The moisture content of the sample is measured by a precision balance. Using the values of these weights, the swelling rate is calculated by the following formula. 20 Swelling rate (wt%) = [(weight after impregnation-weight before impregnation) ) / Weight before immersion] x100 (Hardness) Measured with a Shore A hardness tester with a thickness of 6 mm or more in accordance with JIS K 6253. 120 1222390 发明 Description of the invention (compression rate, compression recovery rate) Processing The latter buffer layer uses a cylindrical indenter with a diameter of 3 IM, and uses TMA manufactured by SII to measure T1 to T3 at 25 ° C, and then calculates it by the following formula. 5 Compression ratio (%) = [(ΤΙ —Τ2 ) / Τ1] χ100 compression response rate (%) = [(Τ3 — Τ2) / (Τ1 — Τ2)] χ100 ΤΙ: from no-load state to load 30kPa (300g / cm 2) The thickness of the polishing layer T2 when the stress is maintained for 60 seconds: From the T1 state to the load of 180kPa and the thickness of 10 layers is polished when the stress is maintained for 60 seconds T3: After the load is released from the T2 state and left for 60 seconds, the load is then 30kPa Thickness of polishing layer when stress was maintained for 60 seconds (evaluation of polishing characteristics) Using SPP600S (manufactured by Okamoto Machine Tool Co., Ltd.) as the polishing device 15, the polishing characteristics of the prepared polishing pads were evaluated. Those who have a 1 μm thermal oxide film formed on the wafer are ground to about 0.5 μm, and the polishing rate is calculated from this time. For the film thickness measurement of the oxide film, an interference film thickness measuring device (made by Otsuka Electronics Co., Ltd.) is used. The property is measured by stylus measurement at 14 points on the polished surface of the wafer polished above, and is calculated by the following formula: 20 Uniformity (%) = 100x (Rmax-Rmin) / (Rmax + Rmin). The conditions are as follows: silicon dioxide slurry SS12 (produced by Cabot Corporation) is added as a polishing liquid at a flow rate of 150 ml / min during grinding. The grinding conditions are the same, the grinding load is 350 g / cm 2, and the number of rotations of the grinding turntable is 35 rpm. Wafer rotation 30 rpm. It can be said that the larger the value is, the better the polishing pad is 121 玖, which is described in the invention. The stability of the polishing rate is evaluated under the same polishing conditions as described above, using several 8-inch silicon wafers to form 1 μm heat. The oxide film was polished for 5 minutes, and then polished with a new silicon wafer for about 0.5 μm, and then the polishing rate was calculated and evaluated. It can be said that the larger the polishing rate, the better the polishing performance. [Preparation of polishing layer] Put 3,000 parts by weight of polyether urethane prepolymer AdipreneL_325 (manufactured by Unilo) into a container, and polysiloxane surfactant SH192 (dimethylsilicone · poly 120 parts by weight of an olefin oxide copolymer, manufactured by Toray Dow Corning Silicone Co., Ltd., and stirred with a blender at about 900 rpm to make a foaming solution. After that, the blender was replaced and the mixture was heated and melted while being hardened. 770 parts by weight of the agent (4,4, -amidino-bis [2-gasaniline]) was put into a foaming solution. After stirring for about 丨 minutes, the mixed liquid was placed in a disc-shaped open mold 'and subjected to secondary hardening at 110 for 6 hours by a heating furnace to form a foamed polyurethane block. Next, the foamed polyurethane block was heated to about 50 ° C, cut with a slicer VGW-125 (manufactured by AMITEC) to a thickness of i.27 mm, and the surface was polished to obtain a polishing layer. Make up tablets. [Production of polishing pad] (Example 11-1) Using the polishing layer (surface shape: porous) prepared as described above, a double-sided tape (double tack tape made by Sekisui Chemical Industry Co., Ltd.) was stuck on the opposite side to the polishing surface. And paste a surface that has been polished and corona treated 1222390 玖, a polyethylene styrofoam (manufactured by Toray Co., Doribov (Transliteration: Bu Yi Bu Yi 7)) (1.27 mm thick) as an invention description The buffer layer is laminated with a double tack tape on the side opposite to the buffer layer's abutting surface to make a grinding pad. (Examples 11 to 2) 5 parts of a buffer layer blended with a styrene-butadiene copolymer (manufactured by JSR, SBR1507) was 84 parts by weight as a polymer, and 10 parts by weight of lauryl methacrylate was used as a monomer. 1 part by weight of dimethyl ketal was used as a photoinitiator, and 5 parts by weight of liquid isoprene was used as a plasticizer. After being melted and mixed by a 2-axis extruder, it was extruded in a T shape. The sheet and the PET film having a thickness of 100 μm are fed into a pinch roller to pressurize and the thickness of the buffer layer is formed to 1.27 legs, and an unhardened buffer layer constituting sheet is formed. The PET film of the unhardened buffer layer constituting sheet is peeled off, and the same abrasive layer is placed on one side of the layer, and then the light is hardened by ultraviolet light from the reverse side to make it adhere. The same double-sided tape as in Example U 15-1 was stuck on the side opposite to the bonding surface of the buffer layer to make a polishing pad. (Examples 11 to 3) Except that a natural rubber foam (Wu Yu supersoft) was used as a buffer layer, a grinding pad was produced in the same manner as in Examples 11 to 1. 20 (Examples 11 to 4) A polishing pad was produced in the same manner as in Examples 11 to 1 except that a polyurethane foam having a foaming ratio of 15 times was used as the buffer layer. (Comparative Example 11-1) Except the use of a ream of 3.5 denier polyester fiber with a basis weight of 123 1222390 玖, a non-woven fabric impregnated with water of 200 g / m2 impregnated with a 30% by weight water-dispersed polyurethane emulsion and The dried layer was used as the buffer layer, and the rest were made in the same manner as in Example 11-1. [Table 11] Example 11-1 Example 11-2 Example 11-3 Example 11-4 Comparative Example 11-1 Buffer layer characteristic swelling ratio (%) 14.3 0.2 24.8 9.6 41.8 Hardness (Xiao Er) 37 17 28 27 56 Compression rate (%) 6.0 20.4 19.5 13.9 15.0 Compression recovery rate (%) 94 93 90 94 73 Evaluation results of polishing pads Polishing rate (A / nim) 2100 2550 2200 2400 1900 Polishing rate after 5 minutes (A / nim ) 2150 2510 2300 2350 2500 Uniformity (%) 7.3 6.7 6.0 7.8 7.1

5 From the results in Table 11, it can be seen that the polishing pad of the present invention having a buffer layer with a swelling ratio of 40% or less of water is excellent in polishing rate, polishing rate after 5 minutes, and uniformity, and the polishing rate is also stable. However, the comparative example polishing pad whose water swelling ratio exceeds 40% fails to meet the requirements of the polishing rate, and the stability of the polishing rate is also poor. 10 Another grinding method of the present invention uses water with a swelling ratio of 40% or less.

As the buffer layer, the polishing rate of the polishing pad changes little after a period of time, and the productivity is high. Industrial Applicability The polishing pad of the present invention can be used as a material that requires high surface flatness, such as polishing of optical materials such as lenses and reflectors15, silicon wafers, glass substrates for hard disks, aluminum substrates, and general metal polishing. A polishing pad that is stable and has a high polishing efficiency for planarization. The polishing pad of the present invention is particularly suitable for flattening silicon wafers and devices (multilayer substrates) on which oxide layers and metal layers are formed, before laminating and forming such oxide layers or metal layers. program. In addition, the polishing pad of the present invention can control scratches (scratches), release clips 124 1222390 玖, description of the invention, and has the advantage of long life. In this way, according to the present invention, a polishing pad having a high polishing rate and excellent flatness and uniformity can be obtained. [Brief Description of the Drawings] 5 FIG. 1 is a schematic diagram showing a semiconductor polishing apparatus. Fig. 2 is a schematic diagram showing the structure of a polishing pad. Figures 3 (a) and (b) show the outline of the method for measuring the dynamic friction coefficient.

Figure [Drawings of ^ Mainly redundant and representative symbols] 13 ··· Covering layer 14 ... Sheet 1 for polishing layer 1 ... Polishing pad 2 ... Grinding disc 3 ... Material to be polished (wafer) ·· Loading table (polishing head) 5 ... Grinding agent supply mechanism 6,7 ·· Rotary shaft 8 ·· Polishing pad 15 ". Glass plate 16.. 19… test sample

9 ... abrasive layer 10 ... buffer layer 11 ... double-sided tape 12 ... double-sided tape adhesive layer 20 ... double-sided tape 21 ... buffer layer 22 .... double-sided tape for resin printing plate fixing 125

Claims (1)

1222390, g cotton ¥ fiscal day pick up, patent application scope No. 91123212 Patent application patent scope amendment May 24, 1993 1. A polishing pad, a semiconductor polishing pad whose polishing layer is an independent bubble resin foam The number of bubbles of the independent bubbles in the aforementioned polishing layer is 200 pieces / mm 2 or more and 2,000 pieces / dirty 2 or less. 5 2 · —A polishing pad is a semiconductor polishing pad in which the polishing layer is a closed cell resin foam, and the average cell diameter of the closed cells in the foregoing polishing layer is 30 μm to 60 μm. 3 · —A kind of polishing pad, which is a semiconductor polishing pad whose polishing layer is a closed-cell resin foam, and the number of closed-cell bubbles in the above-mentioned polishing layer is 200/10 mm 2 or more and 600 / leg 2 or less. The average cell diameter is 30 μm to 60 μm. 4. A polishing pad having a polishing layer made of a resin foam and having a thermal dimensional change rate of the polishing layer of 3% or less. 5 · —A polishing pad having a polishing layer composed of a resin foam, and the kinetic friction coefficient of the surface of the above-mentioned polishing layer is within a range of 0.1 to 1.0. 6. Kinds of abrasives are those with a resin layer, and the abrasion difference between the abrasion test before and after the abrasion test before and after the 24-hour immersion test in a 12.5 potassium hydroxide aqueous solution (4 (TC)). 10 mg or less. 7. The polishing pad according to any one of items i to 6 of the patent application scope, wherein the storage elastic modulus of the 20 resin foam or the resin layer at 40 ° C is 270 MPa or more. 8. The polishing pad according to any one of the items 1 to 6 of the patent application scope, wherein the resin foam or the resin layer is a polyurethane resin foam. 9. The item 8 of the patent application scope The polishing pad, in which the polyurethane tree 126 is applied for patent application ^ ^ ^ ^ ^ The density of the fat foam is in the range of 0.67 g / on 3 to 0.90 g / cm 3 10. The polishing pad according to item 8 of the scope of the patent application, wherein the polyurethane resin foaming system contains 0.05 to 5 wt% of a polyoxyl-based surfactant. 11. The scope of the patent application 10 polishing pads, in which the polysiloxane surfactant is a copolymer of polyalkylsiloxane and polyether. The grinding pad of any one of items 1 to 6, wherein the hardness of the abrasive layer is 45 or more and less than 65.0 U as measured by a D-type rubber hardness meter. The polishing pad has a compression ratio of 0.5% or more and 5% or less of the polishing layer. 14. The polishing pad according to any one of claims 1 to 6, wherein the polishing layer is laminated on the polishing layer. A soft buffer layer to form a structure of at least two layers. 15. The polishing pad of item 14 in the scope of the patent application, wherein the buffer layer is selected from the group consisting of a polyester non-woven fabric and a polyurethane hair. Foam or polyethylene foam. 16 · —A method for polishing semiconductor wafers, while rotating the polishing pad described in any one of items 1 to 6 of the scope of application for a patent and contacting it with the semiconductor wafer, A polishing agent is supplied and polished between the polishing layer and the semiconductor wafer. P. The polishing method for a semiconductor wafer according to item 16 of the patent application range, wherein the polishing layer contains 0.05 wt% to 5 wt. Surfactant-based polyurethane resin foam. 1222390 Patent application scope A method of manufacturing a polishing pad according to item 10 of the patent scope, which includes a process for producing polyurethane foam, that is, a process that contains, contains isocyanate-containing compounds At least one of the first component or the second component containing an active hydrogen group-containing compound is added in an amount of 0.05% to 5% by weight based on the total amount of the first component and the second component 5. It is a surfactant, and then the components added with the aforementioned surfactant and the non-reactive agent are used to make the bubble dispersion liquid in which the foregoing non-reactive gas fine bubbles are dispersed, and then the remaining ingredients are mixed in the bubble dispersion liquid and used. Its hardened. 10 19. A method for manufacturing a foamed polyurethane polishing pad, which comprises adding a polyionic surfactant to an isocyanate S-terminated prepolymer and stirring to form bubbles in the presence of a non-reactive gas The stirring procedure of the dispersion liquid, a mixing procedure of adding a chain extender to the aforementioned bubble dispersion liquid to form a foaming reaction solution, and a hardening procedure of the aforementioned reaction hardening of the foaming reaction solution, and the isocyanate terminal is described. The isocyanate monomer content of the prepolymer is 20% by weight or less. φ 20 · A method for manufacturing a foamed polyurethane polishing pad according to item 9 of the scope of the patent application, wherein the isocyanate-terminated prepolymer uses at least one of aliphatic diisocyanate and alicyclic diisocyanate. Species (a first isocyanate ° component) and an aromatic diisocyanate (a second isocyanate component) as the isocyanate component, and the ratio in the isocyanate monomer is the aforementioned first isocyanate component / second isocyanate component = 0.5 to 3.2 ( (Weight ratio) 〇21 · For example, the manufacturing of foamed polyurethane polishing pad No. 20 in the scope of patent application 128 1222390, the method of manufacturing patent scope, wherein the first isooxy acid ester component is 4,4, -Manufacturing of dicyclohexyl oxane diisocyanate, and the aforementioned second isocyanate component is toluene diisocyanate. 22 · The manufacture of a foamed poly (urethane) 5 ester polishing pad as described in any one of claims 19 to 21 The method, wherein the added amount of the polysiloxane surfactant in the stirring procedure is in the range of 0.05 wt% to 5 wt%. 23 · —A polishing pad formed by using a polyaminocyanate composed of an organic polyisocyanate, a polyhydric alcohol, and a hardener as the main constituent raw materials. The main component of the aforementioned hardener is 4,4, and fluorenylbis ( O-chloroaniline), and the number-average molecular weight of the aforementioned polyvalent 10 alcohol is in the range of 500 to 1600, and it contains polytetramethylene glycol having a molecular weight distribution (weight average molecular weight / number average molecular weight) of less than 1.9. 24. A kind of polishing pad, which contains an abrasive layer using a polymer material as a matrix material, and the polymer material has a swelling degree of 2% to 15 when immersed in a second-generation pH11 sodium hydroxide aqueous solution for 15 hours. Within the range of%. & The grinding mill according to item 24 of the application, wherein the polymer material is a polyurethane compound and a water-soluble polymer polyol as a polyol compound as a constituent of the polyurethane. 〇 26 · # Grinding 塾 is a grinding layer with a polymer material as the matrix material, and the contact angle of the molecular material to water is 70. ~ 95. Within range. · If you apply for a June patent, you can grind the item No. 26, where the polymer material is polyurethane, and the polyurethane is mainly poly-polyol, and the aforementioned Actinide polyols—part of them are water soluble 129 1222390. Glycols with patent application scope. 28. The polishing pad according to claim 25 or 27, wherein the polyurethane is a foamed polyurethane containing fine bubbles. 29. If the polishing pad of item 28 of the patent application scope, the density of the foaming polyurethane + 5 is in the range of 0.67 g / cni 3 to 0.90 g / cm 3. 30. The polishing pad according to item 28 in the scope of the patent application, wherein the foamed polyurethane system contains 0.1 wt% to 5 wt% polymer > 6 oxygen-based surfactant. 31. The polishing pad according to item 24 or 26 of the patent application scope, wherein the storage elastic modulus of the polishing layer at 40 ° C is 270Mpa or more. 32 · —A method for manufacturing a grinding mill which applies to the scope of patent application No. 30, which includes a process for manufacturing a micro-foamed polyurethane, that is, a first component containing a δ-isocyanate-containing compound Or at least one of the second component containing an active hydrogen group-containing compound is added to the total weight of the first component and the second component in an amount of 0.1 wt% to 5 wt% without a radical-containing polysilicone oxygen-based surfactant 15 , i, meaning 'then mix the component added with the aforementioned surfactant and the non-reactive gas to prepare a bubble dispersion liquid in which the non-reactive gas is dispersed as fine bubbles, and then mix the remaining components in the bubble dispersion And harden it. 33 · —A method for manufacturing a polishing pad, the polishing pad having a polishing layer composed of a foamed polyurethane containing fine gas, and a contact angle of the foamed polyurethane Tied to 70. Within the range of ~ 95 ^ ', and the manufacturing method of the polishing pad includes the following procedures, namely: (1) Stirring procedure, which is based on isocyanate-terminated prepolymer added with a polysiloxane surfactant, and in the presence of non-reactive gas Stirring to form gas 130, apply for patented bubble dispersion; (2) mixing procedure, adding a chain extender to the aforementioned bubble dispersion, and mixing to form a foaming reaction solution; (3) hardening procedure, which causes the aforementioned foaming The reaction solution hardens. 5 34 The method of manufacturing a polishing pad according to Item 33 of Shishen's Patent, which includes a lamination procedure of laminating a flexible porous sheet on the above-mentioned polishing layer. 35_ 'Grinding abrasive' has at least a polishing layer and a buffer. Layer, and the swelling ratio of the buffer layer to water is 40% or less. 36. The polishing pad of item% of the scope of application, wherein the buffer layer is a resin foam of an independent bubble type. 37. The polishing pad according to claim 35, wherein the buffer layer is a non-foaming resin. 38. The grinding chuck according to any one of claims 35 to 37 in the scope of the patent of Shenyin, which is used for grinding semiconductor wafers or glass substrates for precision machines. 131