WO2012141327A1 - 研磨パッド及びその製造方法 - Google Patents
研磨パッド及びその製造方法 Download PDFInfo
- Publication number
- WO2012141327A1 WO2012141327A1 PCT/JP2012/060273 JP2012060273W WO2012141327A1 WO 2012141327 A1 WO2012141327 A1 WO 2012141327A1 JP 2012060273 W JP2012060273 W JP 2012060273W WO 2012141327 A1 WO2012141327 A1 WO 2012141327A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- polishing pad
- compound
- polyurea resin
- polyurethane polyurea
- Prior art date
Links
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/22—Lapping pads for working plane surfaces characterised by a multi-layered structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
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- B24B37/11—Lapping tools
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- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Definitions
- the present invention relates to a polishing pad.
- the present invention relates to a polishing pad for CMP of a semiconductor device.
- the free abrasive grain method is a method of polishing a processed surface of an object to be polished while supplying a slurry (polishing liquid) containing abrasive grains between a polishing pad and a non-polishing object.
- a polishing pad for a semiconductor device requires an opening for holding abrasive grains on the polishing pad surface, hardness to maintain the flatness of the surface of the semiconductor device, and elasticity to prevent scratches on the surface of the semiconductor device. Is done.
- a polishing pad having a polishing layer manufactured from a urethane resin foam is used as a polishing pad that meets these requirements.
- the urethane resin foam is usually cured and molded by a reaction between a prepolymer containing an isocyanate group-containing compound and a curing agent (dry method). And a polishing pad is formed by slicing this foam in a sheet form.
- a polishing pad having a hard polishing layer formed by a dry method in this manner (hereinafter, sometimes abbreviated as a hard (dry) polishing pad) is a relatively small, substantially spherical bubble inside the foam during urethane resin curing molding. Therefore, an opening (opening) that can hold the slurry during polishing is formed on the polishing surface of the polishing pad formed by slicing.
- the urethane resin foam used as a material for polishing pads for semiconductor devices has been mainly used in the vicinity of 30 ⁇ m with a bubble diameter of 100 ⁇ m or less (Patent Document 1). Further, urethane resin foams having a hardness of 70 degrees or more and a D hardness of 45 degrees or more are mainly used (Patent Documents 2 to 3), and the density is 0.5 g / cm 3 or more (Patent Document 1). ), And those having a storage elastic modulus of several hundred MPa or more (Patent Document 4). About the longitudinal elastic modulus (Young's modulus), 500 MPa or more was the mainstream (Patent Document 5).
- the dry polishing pad described above is still hard, and since it is easy to apply pressure locally to the object to be polished, it is satisfactory in terms of reducing scratches generated on the surface of the object to be polished. It wasn't. Moreover, it still had the problem of being easily clogged. Therefore, after polishing with a hard polishing pad formed by these dry methods, it is usually necessary to perform final polishing using a polishing pad having a soft polishing layer formed by a wet method (wet method). Is a method in which a resin solution in which a resin is dissolved in a water-miscible organic solvent is applied to a sheet-like film-forming substrate and then the resin is coagulated and regenerated in an aqueous coagulating liquid).
- a polishing pad having a soft polishing layer formed by a wet method has low hardness and large suede type openings, and its foam structure is also non-uniform. Therefore, it is superior in polishing rate and polishing uniformity (uniformity: the pad surface can follow the undulation and warpage of the object to be polished) compared to polishing with a polishing pad having a hard polishing layer formed by a dry method. Since the foam shape is anisotropic, the opening state of the surface changes due to wear, or the low density part under the polishing layer is torn off, and it is impossible to maintain a constant polishing state for a long time Had a point.
- the present invention has been made in view of the above-mentioned problems, improves the problem of scratches that occur when a conventional hard (dry) polishing pad is used, is excellent in polishing rate and polishing uniformity, and is only for primary polishing.
- An object of the present invention is to provide a polishing pad that can cope with finish polishing as well as a method for manufacturing the same.
- the present invention employs the following configuration.
- a polishing pad comprising a polishing layer having a polyurethane polyurea resin foam containing substantially spherical cells,
- the longitudinal elastic modulus E of the polyurethane polyurea resin foam is in the range of 450 to 30000 kPa, and the density D of the polyurethane polyurea resin foam is in the range of 0.30 to 0.60 g / cm 3.
- a polishing pad for polishing a semiconductor device is
- Mda represents the average molecular weight per bifunctional amino group of the polyamine compound constituting the polyurethane polyurea resin
- r represents the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound constituting the polyurethane polyurea resin. . )
- Isocyanate group-containing compound (A), polyisocyanate compound (B), polyamine compound (D), mixed liquid (E) containing water, foam stabilizer and reaction catalyst, and non-reactive with respect to each component A preparation step of preparing the gas; At least the isocyanate group-containing compound (A), the polyisocyanate compound (B), the polyamine compound (D), a mixed liquid (E) containing water, a foam stabilizer and a reaction catalyst, A mixing step of mixing with a reactive gas to obtain a mixture for forming a foam; A foam molding step of molding a polyurethane polyurea resin foam from the foam molding liquid mixture; and a polishing layer for forming a polishing layer having a polishing surface for polishing an object to be polished from the polyurethane polyurea resin foam 8.
- the equivalent ratio of the amino group of the polyamine compound (D) to the sum of the equivalents of the amino group of the polyamine compound (D) and the hydroxyl group of the polyol compound (C-2) (equivalent of active hydrogen group) 10.
- the polyamine compound (D) is a mixture of a monomer and a multimer of methylene bis-o-chloroaniline (MOCA), and is a crude MOCA containing 15% by mass or more of the multimer.
- the polishing pad of the present invention has a low longitudinal elastic modulus E, strong pressing against an object to be polished is suppressed, and scratches (scratches) are hardly caused.
- the porosity is high (the density is small), scratches due to clogging are less likely to occur.
- it is softer than a polishing pad having a polishing layer formed by a conventional dry method, it is excellent in polishing rate and polishing uniformity.
- the abrasion speed of the polishing surface is slower than that of a wet-molded polishing pad, and the change in the bubble diameter in the depth direction is small, so that a constant polishing state can be maintained for a long time. I can do it. Therefore, even a dry-molded polishing pad can be advantageously used for both primary processing and finishing.
- Sectional drawing (left side) of the polishing pad which shows embodiment of this invention and sectional drawing (right side) of the polishing pad (comparative example 1) which has the polishing layer dry-molded by the prior art.
- the polishing pad of the present invention is a polishing pad containing a polishing layer having a polyurethane polyurea resin foam containing substantially spherical cells, wherein the polyurethane polyurea resin foam has a longitudinal elastic modulus E in the range of 450 to 30000 kPa. And the polyurethane polyurea resin foam has a density D in the range of 0.30 to 0.60 g / cm 3 .
- the polyurethane polyurea resin foam means a resin foam having at least two urethane bonds and at least two urea bonds in the molecule.
- the polyurethane polyurea resin foam of the present invention comprises an isocyanate group-containing compound formed by reacting a polyisocyanate compound and a polyol compound, a polyisocyanate compound, a polyamine compound, and a mixed liquid containing water, a foam stabilizer and a reaction catalyst ( Hereinafter, it may be abbreviated as an aqueous dispersion).
- the substantially spherical shape is a concept that means a normal bubble shape (isotropic, spherical, elliptical, or a shape close to these) present in a foam molded by a dry method (see FIG. 1) and bubbles contained in a foam molded by a wet method (which has anisotropy and has a structure in which the diameter increases from the polishing layer surface to the bottom of the polishing pad) are clearly distinguished.
- the longitudinal elastic modulus (Young's modulus) E is measured on a test piece of 10 mm ⁇ 60 mm (distance between clamps 30 mm) at a tensile speed of 0.5 mm. This is a coefficient when each strain ⁇ , that is, [test piece length at each test force (mm) ⁇ 30 mm] / 30 mm] is obtained in the range of test force 50 gf to 150 gf and linear approximation is performed by the least square method.
- the polyurethane polyurea resin foam has a longitudinal elastic modulus (Young's modulus) E of 450 to 30000 kPa, more preferably 750 to 25000 kPa, and most preferably 900 to 21000 kPa.
- the longitudinal elastic modulus within the above range is a very low value as compared with a polishing pad having a conventional dry-formed polishing layer. If the longitudinal elastic modulus E is within this range, strong pressing of the polishing pad against the object to be polished is suppressed, and scratches (scratches) are less likely to occur on the polishing surface (processed surface) of the object to be polished. In addition, the polishing rate and polishing uniformity can be improved.
- the polyurethane polyurea resin foam has a density D of 0.30 to 0.60 g / cm 3 , more preferably 0.35 to 0.55 g / cm 3 , and 0.35 to 0.50 g / cm 3. Even more preferably.
- the density D is within the above range, scratches due to clogging of the surface of the polishing layer due to abrasives or processing waste of the object to be polished are less likely to occur.
- the density D is smaller than the lower limit, the elasticity becomes extremely large, so that the pad itself is greatly deformed when it comes into contact with the object to be polished, and the planarization performance is deteriorated.
- it becomes larger than the upper limit value scratches are generated due to lack of elasticity.
- both the longitudinal elastic modulus E and the density D are limited to the above numerical ranges, a polishing pad that is good in all aspects of suppressing the occurrence of scratches, polishing rate, and polishing uniformity. Can be obtained.
- the Z value means that factors such as HSC, density, and bubble diameter, which affect the characteristics such as scratches, rate, and flatness, influence each other, not the individual, and bring about the optimum value.
- HSC 100 ⁇ (r ⁇ 1) ⁇ (Mdi + Mda) ⁇ (Mg + r ⁇ Mdi + (r ⁇ 1) ⁇ Mda) (1)
- Mdi represents the average molecular weight per difunctional isocyanate group of the polyisocyanate compound constituting the polyurethane polyurea resin
- Mg represents the average molecular weight per difunctional hydroxyl group of the polyol compound constituting the polyurethane polyurea resin
- Mda represents the average molecular weight per amino group bifunctionality of the polyamine compound constituting the polyurethane polyurea resin
- r represents the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound constituting the polyurethane polyurea resin.
- the hard segment content (HSC) (%) of the present invention will be described.
- the polyurethane polyurea resin is formed by reacting an excess polyisocyanate compound and a polyamine compound by adding a polyamine compound after the prepolymer is formed and a soft segment of the prepolymer formed by the reaction of the polyisocyanate compound and the polyol compound.
- a block copolymer composed of a hard segment (urea segment) in the present invention, a urethane bond of a polyurethane polyurea resin is regarded as a soft segment).
- a urea bond exists between the polyisocyanate compound and the polyamine compound.
- this urea bond forms a strong hydrogen bond with respect to the urethane bond, the more the urea bond is, the more the aggregation due to the hydrogen bond occurs between the plurality of hard segments, thereby forming a hard crystal layer. Further, the denser the urea bonds (regular polyurea segment), the stronger the cohesive force with the segment of the adjacent molecule, and the stronger the crystalline layer is formed. On the other hand, when the proportion of the soft segment is high (that is, the proportion of the polyol compound is high), the mobility becomes high and the soft segment is softened. Therefore, the hardness of the polishing layer can be adjusted by the value of HSC (for example, PJ Flory; Journal of American Chemical Society, 58, 1877-1885 (1936).
- HSC for example, PJ Flory; Journal of American Chemical Society, 58, 1877-1885 (1936).
- the HSC can be calculated by obtaining Mdi, Mg, Mda, r by structural analysis such as nuclear magnetic resonance (NMR) spectrum of the polyurethane polyurea resin constituting the polishing layer.
- NMR nuclear magnetic resonance
- the object to be polished can be polished without causing scratches. ,preferable. Further, since the surface is softened, it is possible to follow the surface shape of the object to be polished, the polishing rate is increased, and the polishing uniformity is improved. On the other hand, it is possible to ensure a certain leveling ability of an object to be polished. The reason why the above effect is exhibited when the Z value is within the above range is unknown, but it is presumed that the surface of the polishing layer becomes softer when the polishing pad is used, while the inner surface is kept hard.
- the average bubble diameter is an average value of equivalent circle diameters calculated from the area and the number of each bubble portion obtained by binarizing the surface image of the polishing pad (however, (This is a numerical value when the “cut-off value” is set to 10 ⁇ m for noise cut during image processing).
- the average cell diameter d ( ⁇ m) of the polyurethane polyurea resin foam of the polishing layer is preferably 120 to 185 ⁇ m, and more preferably 140 to 170 ⁇ m. If the average bubble diameter ( ⁇ m) is greater than or equal to the upper limit value, the polishing layer surface becomes rough and the polishing quality of the object to be polished deteriorates. If the average bubble diameter is less than the lower limit value, the polishing layer surface is clogged or the polishing layer surface is flexible. It loses its properties and scratches easily occur.
- the A hardness means a value measured according to JIS K7311.
- the D hardness means a value measured according to JIS K6253-1997 / ISO 7619.
- the A hardness of the polyurethane polyurea resin foam is preferably 20 to 55 degrees.
- the D hardness of the polyurethane polyurea resin foam is preferably 5 to 35 degrees. If the A hardness and / or D hardness is smaller than the above range, the elasticity becomes extremely large, so that the pad itself is greatly deformed when it comes into contact with the object to be polished, resulting in poor flattening performance. On the other hand, when it becomes larger than the above range, scratches are generated due to lack of elasticity.
- the storage elastic modulus E ′ is the storage at 40 ° C. at an initial load of 10 g, a strain range of 0.01 to 4%, and a measurement frequency of 0.2 Hz according to JIS K7244-4.
- the polyurethane polyurea resin foam preferably has an initial load of 10 g, a strain range of 0.01 to 4%, a measurement frequency of 0.2 Hz, and a storage elastic modulus E ′ in a tensile mode of 1 to 30 MPa. More preferably, it is 1 to 20 MPa.
- the polishing pad of the present invention can be suitably used for polishing semiconductor devices, particularly chemical mechanical polishing (CMP) of semiconductor devices.
- CMP chemical mechanical polishing
- the method for producing a polishing pad for polishing a semiconductor device of the present invention comprises an isocyanate group-containing compound (A), a polyisocyanate compound (B), a polyamine compound (D ), Aqueous dispersion (mixture containing water, foam stabilizer and reaction catalyst) (E), and a preparatory step of preparing a non-reactive gas for each component; at least the isocyanate group-containing compound (A)
- ⁇ Preparation process> In the production of the polishing pad of the present invention, at least the isocyanate group-containing compound (A), the polyisocyanate compound (B), the polyamine compound (D), the aqueous dispersion (E), and the raw material of the polyurethane polyurea resin foam, Nonreactive gases are used for these components. Furthermore, you may use a polyol compound with the said component. Moreover, you may use together components other than the above in the range which does not impair the effect of this invention. Hereinafter, each component will be described.
- the isocyanate group-containing compound as a prepolymer is obtained by reacting the following polyisocyanate compound with a polyol compound under conditions usually used. Moreover, the other component may be contained in the isocyanate group containing compound within the range which does not impair the effect of this invention.
- the isocyanate group-containing compound a commercially available one may be used, or a compound synthesized by reacting a polyisocyanate compound and a polyol compound may be used.
- a polyisocyanate compound heated to 50 ° C. is added to a polyol compound heated to 40 ° C. while stirring in a nitrogen atmosphere, and after 30 minutes, the temperature is raised to 80 ° C. and further reacted at 80 ° C. for 60 minutes. It can be manufactured by such a method.
- the polyisocyanate compound means a compound having two or more isocyanate groups in the molecule.
- the polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule.
- diisocyanate compounds having two isocyanate groups in the molecule include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate (2,6-TDI), 2,4-tolylene diisocyanate (2 , 4-TDI), naphthalene-1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), 4,4′-methylene-bis (cyclohexyl isocyanate) (hydrogenated MDI), 3,3′-dimethoxy -4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate , Propylene-1
- polyisocyanate compound a diisocyanate compound is preferable, among which 2,4-TDI and MDI are more preferable, and 2,4-TDI is particularly preferable.
- These polyisocyanate compounds may be used alone or in combination with a plurality of polyisocyanate compounds.
- the polyol compound means a compound having two or more alcoholic hydroxyl groups (OH) in the molecule.
- (C-1) Polyol compound for prepolymer synthesis Polyol compounds used for the synthesis of isocyanate group-containing compounds as prepolymers include diol compounds such as ethylene glycol and butylene glycol, triol compounds, etc .; polyether polyol compounds such as polytetramethylene glycol (PTMG); ethylene glycol and adipic acid And polyester polyol compounds such as a reaction product of styrene and a reaction product of butylene glycol and adipic acid; a polycarbonate polyol compound and a polycaprolactone polyol compound.
- PTMG is preferred, PTMG having a number average molecular weight (Mn) of about 500 to 5000 is even more preferred, and PTMG of about 1000 is most preferred.
- the above polyol compounds may be used alone or in combination with a plurality of polyol compounds.
- Molecular weight of compound)-(number of functional groups per molecule of polyol compound (C-1) ⁇ mass (parts) of polyol compound (C-1) / molecular weight of polyol compound (C-1))] ”
- the NCO equivalent is a numerical value indicating the molecular weight of PP (prepolymer) per NCO group, and can be used as an index for calculating the ratio of “soft segment / hard segment”.
- the NCO equivalent is preferably 400 to 650.
- a polyol compound is added into the mixer together with the isocyanate group-containing compound, the polyisocyanate compound, the polyamine compound, and the like. Can be mixed.
- the polyol compound may be prepared by itself, but may be prepared as a mixed solution with a polyamine compound, or may be added when preparing an aqueous dispersion.
- the polyol compound acts as a curing agent for curing the prepolymer, and is incorporated in a competitive reaction with the polyamine compound, thereby suppressing a biased chain extension reaction in the block of the polyamine compound, and causing polymerization with less polymerization degree unevenness. It becomes easy to do.
- any compound such as a diol compound or a triol compound can be used without particular limitation. Moreover, it may be the same as or different from the polyol compound used to form the prepolymer. Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3 -Low molecular weight polydiols such as methyl-1,5-pentanediol and 1,6-hexanediol, and high molecular weight polyol compounds such as polytetramethylene glycol, polyethylene glycol and polypropylene glycol.
- bifunctional, trifunctional polypropylene glycol PPG
- trifunctional polypropylene glycol is Polytetramethylene glycol
- the number average molecular weight (Mn) is about 500 to 5000 and / or polytetramethylene glycol. More preferably, polypropylene glycol having a Mn of about 2000 to 4000 and / or polytetramethylene glycol having a Mn of about 500 to 1500, and a polypropylene glycol having a Mn of about 3000 and / or a polytetramethylene glycol having a Mn of about 1000. But most preferred.
- the polypropylene glycol is preferably trifunctional polypropylene glycol.
- the polyol compound (C-2) may be used alone, or a plurality of polyol compounds (C-2) may be used in combination.
- the amino group of the polyamine compound described later and the equivalent of the hydroxyl group of the polyol compound prepared separately from the isocyanate group-containing compound (equivalent of active hydrogen group) It is preferable to prepare such that the equivalent ratio of amino groups of the polyamine compound (hereinafter sometimes referred to as s value) is 0.70 to 0.97 (amino group / (amino group + hydroxyl group)).
- s value the equivalent ratio of amino groups of the polyamine compound
- the polyamine compound means a compound having two or more amino groups in the molecule.
- the polyamine compound acts as a chain extender, and part of the polyamine compound reacts with the polyisocyanate compound to form a hard segment, while part of the polyamine compound binds to the end of the main chain of the isocyanate group-containing compound (soft segment part).
- the polymer chain can be further extended.
- the polyurethane polyurea resin which has the block copolymer of a hard segment and a soft segment is produced
- the polyamine compound an aliphatic or aromatic polyamine compound, in particular, a diamine compound can be used.
- the polyamine compound may have a hydroxyl group. Examples of such amine compounds include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, and di-2-hydroxy.
- Examples include ethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine.
- a diamine compound is preferable, MOCA, diaminodiphenylmethane, and diaminodiphenylsulfone are more preferable, and MOCA is particularly preferable.
- Solid MOCA means pure MOCA in solid form at room temperature.
- Crude MOCA is a mixture of MOCA monomer and MOCA multimer, preferably having a multimer ratio of 15% by mass or more. The ratio of the multimer is more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass. Examples of multimers include MOCA dimers, trimers, and tetramers.
- Crude MOCA makes it easy to control the reaction rate, and as a result, it is easy to obtain uniformity of physical properties of the entire foam (for example, density, hardness, etc.).
- the polyamine compound may be used alone or in combination with a plurality of polyamine compounds.
- solid MOCA and crude MOCA are solid at normal temperature, when used in the mixing step, it is necessary to heat them to about 120 ° C. to bring them into a molten state. Therefore, when the polyol compound (C-2) is used, if MOCA, particularly crude MOCA is dissolved in the polyol compound (C-2) in advance, it can be used in the mixing step without heating to the melting temperature. It is preferable because polymerization spots caused by increased reactivity due to heating are suppressed.
- the mass ratio of MOCA and polyol compound (C-2) is preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, and 1: 1 is preferable.
- the polyol compound (C-2) for dissolving MOCA is preferably polytetramethylene glycol, more preferably a polytetramethylene glycol having a number average molecular weight (Mn) of about 500 to 5000, and an Mn of about 500 to 1500. Polytetramethylene glycol is more preferred, and polytetramethylene glycol having an Mn of about 1000 is most preferred.
- the polyamine compound is preferably degassed under reduced pressure in a heated state as necessary in order to facilitate mixing with other components and / or to improve the uniformity of the bubble diameter in the subsequent foam formation step.
- a defoaming method under reduced pressure a known method may be used in the production of polyurethane polyurea. For example, defoaming can be performed at a vacuum degree of 0.1 MPa or less using a vacuum pump. When a solid compound is used as the chain extender, it can be degassed under reduced pressure while being melted by heating. On the other hand, when using a liquid polyamine compound at room temperature, degassing may be performed under reduced pressure without heating.
- the content ratio (molar ratio or equivalent ratio) of the polyamine compound to the polyol compound and / or the total polyol compound used for prepolymer formation is the content ratio used in the production of a conventional polishing pad. Is much smaller than.
- the HSC of the conventional polishing pad is 35% or more, whereas it is less than 35% in the present invention. In particular, 25 to 35% is preferable, 26 to 34% is more preferable, and 27 to 32% is even more preferable.
- a polishing pad having a polishing layer having longitudinal elastic modulus E and density D in the range of 450 to 30000 MPa and 0.30 to 0.60 g / cm 3 can be easily produced.
- solid MOCA is used as the polyamine compound, it is preferable to use 150 to 205 parts by mass of solid MOCA with respect to a total of 1000 parts by mass of the polyisocyanate compound and the polyol compound (C-1).
- liquid MOCA (described later in detail)
- the aqueous dispersion means a mixed solution containing water, a foam stabilizer and a reaction catalyst.
- the aqueous dispersion contributes to foaming agent, polyaddition catalyst, foam regulation of foam diameter and foaming uniformity.
- water, reaction catalyst, surfactant and the like are stirred using a general stirring device.
- -It can be prepared by mixing.
- the aqueous dispersion is not limited to a combination of only these three components.
- the water contained in the aqueous dispersion is preferably distilled water from the viewpoint of preventing contamination of impurities.
- Water is preferably used in a proportion of 0.1 to 6 parts by mass, more preferably in a proportion of 0.5 to 5 parts by mass, and a proportion of 1 to 3 parts by mass with respect to 1000 parts by mass of the prepolymer. Even more preferably it is used in
- a known catalyst can be used as the reaction catalyst contained in the aqueous dispersion.
- amine catalysts such as tertiary amines, alcohol amines, ether amines (for example, Toyocat ET), acetates (potassium, calcium), organometallic catalysts and the like can be mentioned.
- bis (2-dimethylaminoethyl) ether (Toyocat ET, manufactured by Tosoh Corporation) is used as a catalyst.
- the amount of the catalyst is not particularly limited, but it is preferably used in a proportion of 0.01 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 1000 parts by mass of the prepolymer.
- the surfactant as the foam stabilizer contained in the aqueous dispersion known ones can be used. Examples thereof include polyether-modified silicone. In this example, SH-193 (manufactured by Dow Corning), which is a kind of silicone surfactant, was used. However, the effect of the present invention is not limited to the use of this surfactant. Absent.
- the amount of the surfactant is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 1000 parts by mass of the prepolymer.
- a known flame retardant, colorant, plasticizer, and the like may be included in the aqueous dispersion as long as the effects of the present invention are not impaired.
- the isocyanate group-containing compound (prepolymer) (A), polyisocyanate compound (B), polyamine compound (D) and aqueous dispersion (E) obtained in the preparation step and prepolymer formation step are mixed in the mixer.
- a non-reactive gas is blown into the components.
- the supplied non-reactive gas is agitated and mixed in the mixer together with the components described above, whereby a foam molding mixed liquid in which bubbles are formed is prepared.
- a mixing process is performed in the state heated to the temperature which can ensure the fluidity
- a prepolymer (isocyanate) solution heated to 30 ° C to 100 ° C. Can be put into a jacketed mixer and stirred at 80 ° C. If necessary, the mixture may be aged in a tank with a jacket with a stirrer.
- the stirring time is appropriately adjusted depending on the number of teeth, the number of rotations, the clearance, etc. of the mixer, and is, for example, 0.5 to 600 seconds.
- the gas can be used without particular limitation as long as it is non-reactive with respect to the above-mentioned components, and examples thereof include air, nitrogen, oxygen, carbon dioxide, helium, and argon.
- the gas supply rate is preferably 0.10 to 4.00 L, more preferably 0.17 to 3.33 L, with respect to 1 kg of the total amount of each component. adjust.
- the polyurethane polyurea resin foam is molded by pouring the foam molding mixture prepared in the mixing step into a mold at 50 to 100 ° C. and foaming and curing.
- the prepolymer, the polyisocyanate compound, and the polyamine compound (and the polyol compound) react to form a polyurethane polyurea resin, whereby the mixed solution is cured.
- carbon contained in the aqueous dispersion is generated by the reaction of the isocyanate groups in the prepolymer with water.
- FIG. 1 a cross-sectional view (left side) of a polishing pad showing an embodiment of the present invention and a cross-sectional view (right side) of a polishing pad (Comparative Example 1) having a polishing layer dry-formed by a conventional technique are the same enlarged.
- Photographed at a magnification ( ⁇ 100) a bar indicated by a white line in the right figure represents a length of 100 ⁇ m.
- ⁇ Polishing layer forming step> The polyurethane polyurea resin foam obtained by the foam molding step is sliced into a sheet to form a polyurethane polyurea sheet. By slicing, an opening is provided on the sheet surface. At this time, in order to form an opening on the surface of the polishing layer which is excellent in wear resistance and hardly clogs, it is preferable to age at 30 to 80 ° C. for about 1 to 2 weeks. This makes it easier to obtain desired elastic characteristics.
- the average cell diameter in the foam is preferably within the above-mentioned range, that is, 120 to 185 ⁇ m, more preferably 140 to 170 ⁇ m.
- the temperature (viscosity) of the prepolymer, the rotation speed of stirring, the air flow rate, the foam stabilizer It can be adjusted within the above range by controlling the type, concentration and mold temperature.
- the polishing layer having the polyurethane polyurea sheet thus obtained is then affixed with a double-sided tape on the surface opposite to the polishing surface of the polishing layer, and is cut into a predetermined shape, preferably a disc shape, The polishing pad of the present invention is completed.
- the double-sided tape is not particularly limited, and any double-sided tape known in the art can be selected and used.
- the polishing pad of the present invention may have a single layer structure consisting only of a polishing layer, and a multilayer in which another layer (lower layer, support layer) is bonded to the surface of the polishing layer opposite to the polishing surface. It may consist of Although the characteristics of the other layers are not particularly limited, it is preferable that a layer harder than the polishing layer (higher A hardness and / or D hardness) is bonded to the opposite surface side of the polishing layer. By providing a layer harder than the polishing layer, it is possible to avoid the minute unevenness of the polishing surface plate from affecting the shape of the polishing surface, and the polishing flatness is further improved. Moreover, generation
- a plurality of layers may be bonded and fixed using a double-sided tape, an adhesive or the like while applying pressure as necessary.
- a double-sided tape, an adhesive or the like there is no restriction
- the polishing pad of the present invention may be subjected to grinding treatment on the surface and / or back surface of the polishing layer or grooving or embossing on the surface as necessary, and the substrate and / or adhesive layer is polished. It may be bonded to the layer, and a light transmission part may be provided.
- limiting in particular in the method of a grinding process It can grind by a well-known method. Specific examples include grinding with sandpaper.
- the polishing pad of the present invention When the polishing pad of the present invention is used, the polishing pad is attached to the polishing surface plate of the polishing machine so that the polishing surface of the polishing layer faces the object to be polished. Then, while supplying the abrasive slurry, the polishing surface plate is rotated to polish the processed surface of the object to be polished.
- the workpiece to be processed by the polishing pad of the present invention include a glass substrate for hard disk, a mother glass for thin display, a semiconductor wafer, and a semiconductor device.
- the polishing pad of this invention is used suitably for processing a semiconductor device.
- the CMP polishing pad of the present invention has a polishing layer containing a polyurethane polyurea resin foam, the polyurethane polyurea resin foam has a longitudinal elastic modulus E of 450 to 30000 kPa, and the polishing layer has a density D of 0. It is set in the range of 30 to 0.60 g / cm 3 .
- a polishing layer made of polyurethane polyurea resin that satisfies the above range has a lower modulus of elasticity and a lower density than a hard polyurethane polishing layer molded by a conventional dry method, and therefore has a lower hardness than conventional ones.
- a pad is obtained. Therefore, strong pressing between the polishing layer and the object to be polished is suppressed, and scratches are hardly generated on the surface of the object to be polished. Also, the polishing rate and polishing uniformity are improved. In addition, since the density of the polishing layer is small, scratches due to clogging of slurry, processing scraps and the like hardly occur.
- the polishing pad of the present invention is provided with openings having a shape obtained by slicing substantially spherical bubbles, and is uniform in the thickness direction and the planar direction of the polishing layer.
- a polishing pad (soft (wet) polishing pad) having an anisotropic foam structure formed by a conventional wet method and having a foam structure with a relatively large suede-type opening. Is different from the pore shape of the polishing layer surface.
- the soft (wet) polishing pad has a structure in which the bubble diameter gradually increases from the polishing surface toward the bottom. Accordingly, when the surface is worn by polishing, the bubble diameter (opening hole diameter) on the surface is increased, so that the surface becomes rough and the polishing quality is deteriorated.
- the bubble is enlarged as it goes toward the bottom, there is a problem that the surface is pulled and worn due to polishing resistance.
- the polishing pad of the present case is formed by a dry method, the bubbles are isotropic, and the above-described problems of the wet polishing pad are hardly generated.
- the polishing pad of the present invention is softer and less dense than the conventional hard (dry) polishing pad, it is possible to suppress the generation of scratches, and excellent in the polishing rate and polishing uniformity. It can be used for finishing as well as processing. Further, when the Z value is limited within a certain range, the polishing rate and the polishing uniformity can be further improved while maintaining the flattening ability to some extent.
- the NCO equivalent weight of PP is “(mass of polyisocyanate compound (part) + mass of polyol compound (C-1) (part)) / [(number of functional groups per molecule of polyisocyanate compound ⁇ polyisocyanate compound Mass (parts) / molecular weight of polyisocyanate compound) ⁇ (number of functional groups per molecule of polyol compound (C-1) ⁇ mass (parts) of polyol compound (C-1) / molecular weight of polyol compound (C-1)) ]
- the s value is the sum of the equivalents of the amino group (D) of the polyamine compound and the hydroxyl group of the polyol compound (C-2) prepared separately from the isocyanate group-containing compound (A) (active It is a numerical value showing the equivalent ratio (amino group / (amino group + hydroxyl group)) of the amino group of the polyamine compound (D) to (equivalent of hydrogen group).
- the crude MOCA used in the following examples and comparative examples is a liquid mixture (hereinafter referred to as liquid MOCA) in which the mass ratio of PTMG1000 and crude MOCA (multimer content 40% by mass) is 1: 1. .
- Comparative Example 1 In Comparative Example 1, a conventionally known hard (dry) polishing pad was manufactured. As the first component prepolymer, 316 parts of 2,4-TDI, 88 parts of hydrogenated MDI, and 539 parts of PTMG having a number average molecular weight of about 1000 were reacted, and then 57 parts of diethylene glycol was added to further react. This was heated to 55 ° C. and degassed under reduced pressure using an isocyanate group-containing urethane prepolymer having a content of 9.0% and an NCO equivalent of 466. Solid MOCA as the second chain extender was melted at 120 ° C. and degassed under reduced pressure.
- a foaming agent (Expancel 551DE) was mixed with the first component so as to be 2% by weight, and the first component: second component was supplied to the mixer at a ratio of 1000 parts: 256 parts by weight.
- the obtained mixed liquid was poured into a mold of 890 ⁇ 890 mm heated to 50 ° C., cured by heating at 100 ° C. for 5 hours, and then the formed polyurethane resin foam was extracted from the mold. Furthermore, this foam was sliced to a thickness of 1.25 mm to produce a urethane sheet, and a polishing pad was obtained.
- Example 1 an isocyanate content obtained by reacting 2,4-TDI (286 parts) as a prepolymer of the first component, PTMG (714 parts) having a number average molecular weight of about 1000 was 7.8%, and an NCO equivalent was 540. This was heated to 55 ° C. using an isocyanate group-containing urethane prepolymer and defoamed under reduced pressure. Solid MOCA was used as the second component chain extender, which was melted at 120 ° C. and degassed under reduced pressure.
- the aqueous dispersion of the third component has a number average molecular weight of 3000, trifunctional PPG (42 parts), water (3 parts), catalyst (Toyocat ET, manufactured by Tosoh Corporation) (1 part), silicone surfactant. (SH-193, manufactured by Dow Corning Co., Ltd.) (1 part) was added, and the mixture was stirred and mixed at 35 ° C. for 1 hour, and then degassed under reduced pressure.
- Example 2 to 4 and Comparative Examples 2 to 5 A polishing pad having a thickness of 1.32 to 1.35 mm was obtained in the same manner as in Example 1 except that the ratio of each component supplied into the mixer was changed as shown in Table 1.
- Example 5 isocyanate having a content of isocyanate of 7.8% and an NCO equivalent of 540 obtained by reacting 2,4-TDI (286 parts) as a prepolymer of the first component and PTMG (714 parts) having a number average molecular weight of about 1000 was used. This was heated to 55 ° C. using a group-containing urethane prepolymer and degassed under reduced pressure. As a second component chain extender, liquid MOCA (234 parts) was degassed under reduced pressure.
- the aqueous dispersion of the third component has a number average molecular weight of 3000, trifunctional PPG (41 parts), water (3 parts), catalyst (Toyocat ET, manufactured by Tosoh Corp.) (1 part), silicone surfactant (SH-193, manufactured by Dow Corning) (4 parts) was added, mixed with stirring, and degassed under reduced pressure.
- the first component: second component: third component was supplied at a flow rate of 80 kg / min to the mixer at a weight ratio of 1000 parts: 234 parts: 49 parts. At this time, air was supplied at a flow rate of 19.1 L / min from the nozzle provided in the stirring rotor in the mixer (that is, 19.1 L of air was supplied for a total of 80 kg of the first to third components). .
- the obtained mixed liquid was poured into a mold and cured at 100 ° C. for 5 hours, and then the formed polyurethane resin foam was extracted from the mold. This foam was sliced to a thickness of 1.28 mm to produce a urethane sheet, and a polishing pad was obtained.
- Example 6 to 9 A polishing pad having a thickness of 1.28 to 1.30 mm was obtained in the same manner as in Example 5 except that the ratio of each component supplied into the mixer was changed as shown in Table 2.
- Example 10 an isocyanate content of 10.0% and an NCO equivalent of 420 were obtained by reacting 2,4-TDI (325 parts) as a first component prepolymer with PTMG (675 parts) having a number average molecular weight of about 1000. This was heated to 55 ° C. using a group-containing urethane prepolymer and degassed under reduced pressure. As a second component chain extender, liquid MOCA (397 parts) was degassed under reduced pressure. The aqueous dispersion of the third component has a number average molecular weight of 3000, trifunctional PPG (43 parts), water (1 part), catalyst (Toyocat ET, manufactured by Tosoh Corporation) (1 part), silicone surfactant.
- the first component: second component: third component were supplied to the mixer at a flow rate of 80 kg / min at a ratio of 1000 parts: 397 parts: 49 parts by weight. At this time, air was supplied into the mixer at a flow rate of 19.1 L / min.
- the obtained mixed liquid was poured into a mold and cured, and then the formed polyurethane resin foam was extracted from the mold. This foam was sliced to a thickness of 1.27 mm to produce a urethane sheet, and a polishing pad was obtained.
- Example 11 to 15 and Comparative Examples 9 to 13 For Examples 11 to 15 and Comparative Examples 9 to 18, a thickness of 1.27 to 1.30 mm was polished in the same manner as in Example 10 except that the ratio of each component was changed as shown in Tables 3 to 4. A pad was manufactured.
- the longitudinal elastic modulus (kPa) is 10 mm x 60 mm (distance 30 mm between clamps) at a tensile speed of 0.5 mm using Shimadzu Corporation Micro Strength Evaluation Tester Shimadzu Micro Autograph MST-I
- the test force was measured, and the strain ⁇ , ie, [test piece length at each test force (mm) ⁇ 30 mm] / 30 mm] was obtained for the range of test force from 50 gf to 150 gf, and linear approximation was performed by the least square method.
- the coefficient was measured.
- the density (g / cm 3 ) was calculated by measuring the weight (g) of a sample cut into a predetermined size and determining the volume (cm 3 ) from the size.
- a hardness was measured using a Shore A durometer in accordance with Japanese Industrial Standard (JIS K 7311).
- JIS K 7311 Japanese Industrial Standard
- the sample was set so that the urethane sheet (thickness of about 1.3 mm) described in the comparative example and the example was overlapped, and the total thickness was at least 4.5 mm.
- the D hardness was measured with a D-type hardness meter manufactured by Teclock Corporation according to JIS K 6253-1997 / ISO 7619.
- the sample was set so that the urethane sheet (thickness of about 1.3 mm) described in the comparative example and the example was overlapped, and the total thickness was at least 4.5 mm.
- Average bubble diameter ( ⁇ m) The number of bubbles per 1 mm 2 was observed by magnifying the range of about 1.3 mm square on the pad surface with a microscope (VH-6300, manufactured by KEYENCE) by 175 times. Is binarized by image processing software (Image Analyzer V20LAB Ver. 1.3, manufactured by Nikon) to check the number of bubbles, and from the area of each bubble, the equivalent circle diameter and the average value (average bubble diameter) was calculated. Note that the cutoff value (lower limit) of the bubble diameter was 10 ⁇ m, and noise components were excluded.
- the storage elastic modulus (E ′ 40 (MPa)) at 40 ° C. is 10 g of initial load according to JIS K7244-4, strain range 0.01 to 4%, measurement frequency 0 according to TS Instrument Japan RSAIII.
- the storage elastic modulus at 40 ° C. at 2 Hz was measured.
- ⁇ Polishing test> About the polishing pad of each Example and the comparative example, it grind
- a substrate uniformity (CV%) of 13%) in which tetraethoxysilane was formed on a 12-inch silicon wafer by CVD so that the insulating film had a thickness of 1 ⁇ m was used.
- the polishing rate is the amount of polishing per minute expressed in thickness (nm), and the average value was obtained from the thickness measurement results at 17 locations for the insulating film of the substrate before and after polishing.
- the thickness was measured in the DBS mode of an optical film thickness measuring device (ASET-F5x, manufactured by KLA Tencor).
- Polishing uniformity was determined from the variation (standard deviation ⁇ average value) of the 17 thickness measurement results.
- Tables 1 to 4 show the results of the polishing test conducted for each of the examples and comparative examples using the above method.
- the result of the polishing test is as follows in terms of commercial value. Evaluated. The polishing rate was evaluated as ⁇ when 200 or more (nm / min), ⁇ when 190 or more and less than 200 (nm / min), and x when less than 190 (nm / min). Polishing uniformity was evaluated by giving 7.0 or less (CV%) as ⁇ , exceeding 7.0 to 8.0 or less (CV%) as ⁇ , and exceeding 8.0 (CV%) as ⁇ .
- the presence / absence of scratches was evaluated as 0 (no sheet) and x (existing 1 or more). Further, with respect to the three types of polishing rate, polishing uniformity, and presence / absence of scratches, preferred examples are those in which ⁇ is 0 to 1 (all three are ⁇ , two are ⁇ , and one is ⁇ ). Example), samples having two or more ⁇ s and samples having even one ⁇ were evaluated as unfavorable examples (comparative examples) in the present invention.
- the polishing pad of the present invention has a low longitudinal elastic modulus E, strong pressing is suppressed and scratches are hardly caused. In addition, since the porosity is high (the density is small), scratches due to clogging are less likely to occur. Furthermore, since it is softer than a polishing pad having a polishing layer formed by a conventional dry method, it is excellent in polishing rate and polishing uniformity. On the other hand, since it is dry-molded, the abrasion speed of the polishing surface is slower than that of a wet-molded polishing pad, and a constant polishing state can be maintained for a long time. Therefore, even a dry-molded polishing pad can be advantageously used for both primary processing and finishing. Therefore, the polishing pad and the manufacturing method thereof of the present invention have industrial applicability.
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Abstract
Description
前記ポリウレタンポリウレア樹脂発泡体の縦弾性係数Eが450~30000kPaの範囲内であり、且つ、前記ポリウレタンポリウレア樹脂発泡体の密度Dが0.30~0.60g/cm3の範囲内であることを特徴とする、半導体デバイス研磨用の研磨パッド。
(式中、Dは密度(g/cm3)を表し、dは平均気泡径(μm)を表し、HSCは下記式(1)により求められるハードセグメント含有率である:
HSC=100×(r-1)×(Mdi+Mda)÷(Mg+r×Mdi+(r-1)×Mda) ・・・(1)
式(1)中、Mdiは前記ポリウレタンポリウレア樹脂を構成するポリイソシアネート化合物のイソシアネート基2官能あたりの平均分子量を表し;Mgは前記ポリウレタンポリウレア樹脂を構成するポリオール化合物の水酸基2官能あたりの平均分子量を表し;Mdaは前記ポリウレタンポリウレア樹脂を構成するポリアミン化合物のアミノ基2官能あたりの平均分子量を表し;rは前記ポリウレタンポリウレア樹脂を構成するポリオール化合物の水酸基に対するポリイソシアネート化合物のイソシアネート基の当量比を表す。)
少なくとも、前記イソシアネート基含有化合物(A)と、ポリイソシアネート化合物(B)と、ポリアミン化合物(D)と、水、整泡剤及び反応触媒を含む混合液(E)と、各成分に対して非反応性の気体とを混合して発泡体成形用混合液を得る混合工程;
前記発泡体成形用混合液からポリウレタンポリウレア樹脂発泡体を成形する発泡体成形工程;及び
前記ポリウレタンポリウレア樹脂発泡体から、被研磨物を研磨加工するための研磨面を有する研磨層を形成する研磨層形成工程、を有することを特徴とする、上記1~7のいずれかに記載の研磨パッドの製造方法。
<<研磨パッド>>
本発明の研磨パッドは、略球状の気泡を含むポリウレタンポリウレア樹脂発泡体を有する研磨層を含有する研磨パッドであって、前記ポリウレタンポリウレア樹脂発泡体の縦弾性係数Eが450~30000kPaの範囲内であり、且つ、前記ポリウレタンポリウレア樹脂発泡体の密度Dが0.30~0.60g/cm3の範囲内であることを特徴とする。
また、略球状とは、乾式法で成形される発泡体に存在する通常の気泡形状(等方性があり、球状、楕円状、あるいはこれらに近い形状である)を意味する概念であり(図1参照)、湿式法で成形される発泡体に含まれる気泡(異方性があり、研磨パッドの研磨層表面から底部に向けて径が大きい構造を有する)とは明確に区別される。
前記ポリウレタンポリウレア樹脂発泡体の縦弾性係数(ヤング率)Eは450~30000kPaであり、750~25000kPaの範囲内であることがより好ましく、900~21000kPaの範囲内であることが最も好ましい。上記範囲内の縦弾性係数は、従来の乾式成形された研磨層を有する研磨パッドに比べて非常に低い値である。そして、縦弾性係数Eがこの範囲内であると、被研磨物に対する研磨パッドの強い押し付けが抑制され、被研磨物の研磨表面(加工表面)に傷(スクラッチ)が生じにくくなる。また、研磨レート及び研磨均一性も向上し得る。
特に好ましくは、縦弾性係数が750~25000kPa、密度が0.30~0.60g/cm3(好ましくは0.35~0.55g/cm3であり、より好ましくは0.35~0.50g/cm3)であるとともに、Z値が3300~5000の範囲のポリウレタンポリウレア樹脂発泡体である。
(式中、Dは密度(g/cm3)を表し、dは平均気泡径(μm)を表し、HSC(ハードセグメント含有率;%)は下記式(1)により求められる値である。)
ここで、Z値は、HSCと密度と気泡径という、夫々が傷、レート、平坦性といった特性を左右する因子が、個々にではなく、お互いに影響しあって最適値をもたらす事を意味し、鋭意研究の結果、Z値が上記範囲にある場合に一定の平坦性を維持しつつ、スクラッチの発生抑制、研磨レート及び研磨均一性を確保することが可能であることを突き止めた。
通常、ポリウレタンポリウレア樹脂は、ポリイソシアネート化合物及びポリオール化合物の反応によって形成されるプレポリマのソフトセグメントと、該プレポリマ形成後にポリアミン化合物を添加して過剰のポリイソシアネート化合物及びポリアミン化合物が反応して形成されるハードセグメント(ウレアセグメント)と、で構成されるブロックコポリマーである(本発明では、ポリウレタンポリウレア樹脂のウレタン結合をソフトセグメントとみなす。)。
ハードセグメントには、ポリイソシアネート化合物とポリアミン化合物との間にウレア結合が存在する。このウレア結合はウレタン結合に対して強い水素結合が形成されるため、ウレア結合が多いほど複数のハードセグメント間で水素結合による凝集が起こり、硬い結晶層を形成する。また、ウレア結合が密集すればするほど(規則性ポリウレアセグメント)、隣接分子の当該セグメントと強い凝集力を及ぼし、より強固な結晶層を形成する。
一方、ソフトセグメントの割合が高い(すなわち、ポリオール化合物の割合が高い)と運動性が高くなり軟質化することになる。従って、HSCの値により、研磨層の硬度を調整することが出来る(上記HSCの計算式(1)については、例えば、P.J.Flory;Journal of American Chemical Society,58,1877-1885(1936)参照)。
なお、HSCは、研磨層を構成するポリウレタンポリウレア樹脂の核磁気共鳴(NMR)スペクトル等の構造解析により、Mdi、Mg、Mda、rを求めて算出することができる。これより、成形後の研磨パッドにおいても、研磨層を構成するポリウレタンポリウレア樹脂のHSCを求めることは可能である。
Z値が上記範囲内である場合に上記効果を奏する理由は不明であるが、研磨パッドの使用時に研磨層の表面がより軟化する一方で内面は硬質のまま保たれるためではないかと推測される。
本明細書及び特許請求の範囲において、平均気泡径とは、研磨パッドの表面画像を二値化処理し、各々の気泡部分の面積と個数から算出した円相当径の平均値である(但し、画像処理時のノイズカットのために「カットオフ値」を10μmに設定したときの数値である)。
前記研磨層のポリウレタンポリウレア樹脂発泡体の平均気泡径d(μm)は、120~185μmであることが好ましく、140~170μmであることがより好ましい。平均気泡径(μm)が上限値以上であると、研磨層表面が粗くなって被研磨物の研磨品質が悪化し、下限値以下であると研磨層表面の目詰まりや、研磨層表面が柔軟性を失い、スクラッチが発生しやすくなる。
本明細書及び特許請求の範囲において、A硬度とは、JIS K7311に準じて測定した値を意味する。
また、D硬度とは、JIS K6253-1997/ISO 7619に準じて測定した値を意味する。
また、前記ポリウレタンポリウレア樹脂発泡体のA硬度は、20~55度であることが好ましい。
同様に、前記ポリウレタンポリウレア樹脂発泡体のD硬度は、5~35度であることが好ましい。
A硬度及び/又はD硬度が上記の範囲より小さくなると、弾性が極度に大きくなるため被研磨物と接触した際にパッド自体が大きく変形し、平坦化性能が悪くなる。一方で上記の範囲より大きくなると、弾性が欠如することによりスクラッチが発生するようになる。
本明細書及び特許請求の範囲において、貯蔵弾性率E’は、JIS K7244-4で準じ初期荷重10g、歪範囲0.01~4%、測定周波数0.2Hz、にて40℃のときの貯蔵弾性率E’である。
前記ポリウレタンポリウレア樹脂発泡体の40℃、初期荷重10g、歪範囲0.01~4%、測定周波数0.2Hz、引っ張りモードにおける貯蔵弾性率E’は1~30MPaであることが好ましく、1~25MPaであることがより好ましく、1~20MPaであることがさらに好ましい。貯蔵弾性率E’が上記の範囲より小さくなると、研磨中に一時的に加わる偏荷重などによりパッド自体が変形しやすくなり、研磨均一性が悪くなる。一方で上記の範囲より大きくなると、弾性が欠如することによりスクラッチが発生するようになる。
上記本発明の半導体デバイス研磨用研磨パッドを製造することの出来る、本発明の半導体デバイス研磨用研磨パッドの製造方法は、イソシアネート基含有化合物(A)、ポリイソシアネート化合物(B)、ポリアミン化合物(D)、水分散液(水、整泡剤及び反応触媒を含む混合液)(E)、及び各成分に対して非反応性の気体を準備する準備工程;少なくとも、前記イソシアネート基含有化合物(A)、ポリイソシアネート化合物(B)、ポリアミン化合物(D)、水分散液(E)、及び各成分に対して非反応性の気体を混合して発泡体成形用の混合液を得る混合工程;前記発泡体成形用混合液からポリウレタンポリウレア樹脂発泡体を成形する発泡体成形工程;及び前記ポリウレタンポリウレア樹脂発泡体から、被研磨物を研磨加工するための研磨面を有する研磨層を形成する研磨層形成工程、を有することを特徴とする。
本発明の研磨パッドの製造には、ポリウレタンポリウレア樹脂発泡体の原料として、少なくとも、イソシアネート基含有化合物(A)、ポリイソシアネート化合物(B)、ポリアミン化合物(D)、水分散液(E)、及びこれらの成分に非反応性の気体が用いられる。更にポリオール化合物を上記成分とともに用いてもよい。
また、本発明の効果を損なわない範囲で、上記以外の成分を併せて用いてもよい。
以下、各成分について説明する。
プレポリマとしてのイソシアネート基含有化合物は、下記ポリイソシアネート化合物とポリオール化合物とを、通常用いられる条件で反応させることにより得られるものである。また、本発明の効果を損なわない範囲内で、他の成分がイソシアネート基含有化合物に含まれていてもよい。
本明細書及び特許請求の範囲において、ポリイソシアネート化合物とは、分子内に2つ以上のイソシアネート基を有する化合物を意味する。
ポリイソシアネート化合物としては、分子内に2つ以上のイソシアネート基を有していれば特に制限されるものではない。例えば、分子内に2つのイソシアネート基を有するジイソシアネート化合物としては、m-フェニレンジイソシアネート、p-フェニレンジイソシアネート、2,6-トリレンジイソシアネート(2,6-TDI)、2,4-トリレンジイソシアネート(2,4-TDI)、ナフタレン-1,4-ジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート(MDI)、4,4’-メチレン-ビス(シクロヘキシルイソシアネート)(水添MDI)、3,3’-ジメトキシ-4,4’-ビフェニルジイソシアネート、3,3’-ジメチルジフェニルメタン-4,4’-ジイソシアネート、キシリレン-1,4-ジイソシアネート、4,4’-ジフェニルプロパンジイソシアネート、トリメチレンジイソシアネート、ヘキサメチレンジイソシアネート、プロピレン-1,2-ジイソシアネート、ブチレン-1,2-ジイソシアネート、シクロヘキシレン-1,2-ジイソシアネート、シクロヘキシレン-1,4-ジイソシアネート、p-フェニレンジイソチオシアネート、キシリレン-1,4-ジイソチオシアネート、エチリジンジイソチオシアネート等を挙げることができる。
ポリイソシアネート化合物としては、ジイソシアネート化合物が好ましく、中でも2,4-TDI、MDIがより好ましく、2,4-TDIが特に好ましい。
これらのポリイソシアネート化合物は、単独で用いてもよく、複数のポリイソシアネート化合物を組み合わせて用いてもよい。
本明細書及び特許請求の範囲において、ポリオール化合物とは、分子内に2つ以上のアルコール性水酸基(OH)を有する化合物を意味する。
((C-1)プレポリマ合成用のポリオール化合物)
プレポリマとしてのイソシアネート基含有化合物の合成に用いられるポリオール化合物としては、エチレングリコール、ブチレングリコール等のジオール化合物、トリオール化合物等;ポリテトラメチレングリコール(PTMG)等のポリエーテルポリオール化合物;エチレングリコールとアジピン酸との反応物やブチレングリコールとアジピン酸との反応物等のポリエステルポリオール化合物;ポリカーボネートポリオール化合物、ポリカプロラクトンポリオール化合物等を挙げることができる。これらの中でもPTMGが好ましく、数平均分子量(Mn)が約500~5000のPTMGがさらにより好ましく、約1000のPTMGが最も好ましい。
また、“(ポリイソシアネート化合物の質量(部)+ポリオール化合物(C-1)の質量(部))/[(ポリイソシアネート化合物1分子当たりの官能基数×ポリイソシアネート化合物の質量(部)/ポリイソシアネート化合物の分子量)-(ポリオール化合物(C-1)1分子当たりの官能基数×ポリオール化合物(C-1)の質量(部)/ポリオール化合物(C-1)の分子量)]”で求められるプレポリマのNCO当量は、NCO基1個当たりのPP(プレポリマ)の分子量を示す数値であり、「ソフトセグメント/ハードセグメント」の比率を図るための一指標として用いることが出来る。該NCO当量は、400~650であることが好ましい。
また、本発明においては、前記プレポリマとしてのイソシアネート基含有化合物を形成するために用いられるポリオール化合物とは別に、イソシアネート基含有化合物、ポリイソシアネート化合物及びポリアミン化合物などとともにポリオール化合物を混合機内に添加して混合することが出来る。前記ポリオール化合物は、それ自体単独で調製されてもよいが、ポリアミン化合物との混合液として調製されてもよく、水分散液を調製する際に添加されてもよい。該ポリオール化合物は、プレポリマを硬化させる硬化剤として作用し、ポリアミン化合物と競争反応的に組み込まれることによって、ポリアミン化合物のブロック内での偏った鎖伸長反応を抑制し、重合度斑の少ない重合がしやすくなる。
具体例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、ペンタンジオール、3-メチル-1,5-ペンタンジオール、1,6-ヘキサンジオールなどの低分子量ポリジオール、ポリテトラメチレングリコール、ポリエチレングリコール、ポリプロピレングリコールなどの高分子量のポリオール化合物などが挙げられる。これらの中でも、混合工程における他成分との相溶性及び得られる気泡の均一性の観点から、2官能性、3官能性のポリプロピレングリコール(PPG)(ここで、3官能性のポリプロピレングリコールとは、多官能基のグリセリンを重合開始剤に用いた分岐を有するポリプロピレングリコールを意味する)、ポリテトラメチレングリコールが好ましく、数平均分子量(Mn)が約500~5000のポリプロピレングリコール及び/又はポリテトラメチレングリコールがより好ましく、Mnが約2000~4000のポリプロピレングリコール及び/又はMnが約500~1500のポリテトラメチレングリコールがさらに好ましく、Mn約3000のポリプロピレングリコール及び/又はMnが約1000のポリテトラメチレングリコールが最も好ましい。また、上記ポリプロピレングリコールとしては、3官能性のポリプロピレングリコールが好ましい。
上記ポリオール化合物(C-2)は単独で用いてもよく、複数のポリオール化合物(C-2)を組み合わせて用いてもよい。
該ポリオール化合物は単独で用いてもよく、複数のポリオール化合物を組み合わせて用いてもよい。
本明細書及び特許請求の範囲において、ポリアミン化合物とは、分子内に2つ以上のアミノ基を有する化合物を意味する。
ポリアミン化合物は、鎖伸長剤として作用し、一部は前記ポリイソシアネート化合物と反応してハードセグメントを形成しつつ、一部は前記イソシアネート基含有化合物(ソフトセグメント部)の主鎖末端側と結合して、ポリマー鎖を更に伸長させることが出来る。これにより、ハードセグメントとソフトセグメントのブロックコポリマーを有するポリウレタンポリウレア樹脂が生成される。
ポリアミン化合物としては、脂肪族や芳香族のポリアミン化合物、特にはジアミン化合物を使用することができ、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、イソホロンジアミン、ジシクロヘキシルメタン-4,4’-ジアミン、3,3’-ジクロロ-4,4’-ジアミノジフェニルメタン(メチレンビス-o-クロロアニリン)(以下、MOCAと略記する。)、MOCAと同様の構造を有するポリアミン化合物等を挙げることができる。また、ポリアミン化合物が水酸基を有していてもよく、このようなアミン系化合物として、例えば、2-ヒドロキシエチルエチレンジアミン、2-ヒドロキシエチルプロピレンジアミン、ジ-2-ヒドロキシエチルエチレンジアミン、ジ-2-ヒドロキシエチルプロピレンジアミン、2-ヒドロキシプロピルエチレンジアミン、ジ-2-ヒドロキシプロピルエチレンジアミン等を挙げることができる。
ポリアミン化合物としては、ジアミン化合物が好ましく、MOCA、ジアミノジフェニルメタン、ジアミノジフェニルスルホンがより好ましく、MOCAが特に好ましい。
本明細書及び特許請求の範囲において、「固形MOCA」及び「粗製MOCA」を用いた場合には、上記の固形MOCA及び粗製MOCAをそれぞれ意味するものする。
鎖伸長剤として固体の化合物を用いる場合は、加熱により溶融させつつ、減圧下脱泡することができる。
一方、室温で液状のポリアミン化合物を用いる場合は、加熱せずに減圧下脱泡を行ってもよい。
また、ポリアミン化合物として固形MOCAを用いる場合には、ポリイソシアネート化合物とポリオール化合物(C-1)の合計1000質量部に対して、固形MOCAを150~205質量部用いることが好ましい。ポリアミン化合物として液状MOCA(詳細は後記する)を用いる場合には、ポリイソシアネート化合物とポリオール化合物(C-1)の合計1000質量部に対して、液状MOCAを200~400質量部用いることが好ましい。
本明細書及び特許請求の範囲において、水分散液とは、水、整泡剤及び反応触媒を含む混合液を意味する。
水分散液は、発泡剤、重付加の触媒、発泡径や発泡均一性の整泡に寄与するものであり、例えば、水、反応触媒、界面活性剤等を一般的な攪拌装置を用いて攪拌・混合することにより調製することが出来る。もちろん、水分散液は、これら3成分の組み合わせのみからなるものに限定されない。
混合工程では、前記準備工程及びプレポリマ形成工程で得られた、イソシアネート基含有化合物(プレポリマ)(A)、ポリイソシアネート化合物(B)、ポリアミン化合物(D)及び水分散液(E)を、混合機内に供給する。このとき、前記各成分に対して非反応性の気体が吹き込まれる。供給された非反応性気体が前記各成分とともに混合機内で攪拌・混合されることにより、内部に気泡が形成された発泡体成形用の混合液が調製される。混合工程は、上記各成分の流動性を確保できる温度に加温した状態で行われる。
例えば、30℃~100℃に加温したプレポリマ(イソシアネート)溶液に固形MOCA(120℃)またはポリオール化合物(C-2)に溶解したMOCA(80℃)、触媒等を含む分散液を温調可能なジャケット付き混合機に投入し、80℃で攪拌することが出来る。必要に応じ攪拌機付きジャケット付きのタンクに混合液を受けて熟成させても良い。攪拌時間は混合機の歯数や回転数、クリアランス等によって適宜調整するが、例えば0.5~600秒である。
前記気体の供給量は、前記各成分の合計量1kgに対して、好ましくは0.10~4.00L、より好ましくは0.17~3.33Lの範囲内になるように供給速度及び時間を調整する。
発泡体成形工程では、前記混合工程で調製された発泡体成形用混合液を50~100℃の型枠内に流し込み、発泡・硬化させることによりポリウレタンポリウレア樹脂発泡体を成形する。このとき、プレポリマ、ポリイソシアネート化合物、ポリアミン化合物(及びポリオール化合物)が反応してポリウレタンポリウレア樹脂が形成することにより、該混合液は硬化する。このとき、水分散液に含まれる水がプレポリマ中のイソシアネート基と反応することで二酸化炭素が発生する。この発生した二酸化炭素及び前記吹き込んだ気体がポリウレタンポリウレア樹脂中に留まることで、図1に示すような略球状の微細な気泡を多数有するポリウレタンポリウレア樹脂発泡体が形成される。
なお、図1において、本発明の実施形態を示す研磨パッドの断面図(左側)、従来技術で乾式成形された研磨層を有する研磨パッド(比較例1)の断面図(右側)は同一の拡大倍率(×100倍)で撮影されており、右図中の白線で示すバーが100μmの長さを表す。
前記発泡体成形工程により得られたポリウレタンポリウレア樹脂発泡体は、シート状にスライスされてポリウレタンポリウレアシートを形成する。スライスされることにより、シート表面に開孔が設けられることになる。このとき、耐摩耗性に優れ目詰まりしにくい研磨層表面の開孔を形成するには、30~80℃にて1時間~2週間程度エイジングすることが好ましい。これにより、所望の弾性特性が得られやすくなる。ここで発泡体中の平均気泡径を前記範囲内、すなわち、120~185μm、さらには140~170μmとすることが好ましく、プレポリマの温度(粘度)、攪拌の回転数、エアー流量、整泡剤の種類や濃度、金型温度のコントロールによって上記範囲内に調整することが出来る。
研削処理の方法に特に制限はなく、公知の方法により研削することができる。具体的には、サンドペーパーによる研削が挙げられる。
溝加工及びエンボス加工の形状に特に制限はなく、例えば、格子型、同心円型、放射型などの形状が挙げられる。
本発明の研磨パッドにより加工される被研磨物としては、ハードディスク用ガラス基板、薄型ディスプレイ用マザーガラス、半導体ウェハ、半導体デバイスなどが挙げられる。中でも、本発明の研磨パッドは、半導体デバイスを加工するのに好適に用いられる。
本発明のCMP用研磨パッドは、ポリウレタンポリウレア樹脂発泡体を含む研磨層を有し、前記ポリウレタンポリウレア樹脂発泡体の縦弾性係数Eが450~30000kPaであり、且つ、前記研磨層の密度Dが0.30~0.60g/cm3の範囲に設定されている。
また、表1~4の各略号は以下のものを意味する。
・2,4-TDI: 2,4-トリレンジイソシアネート
・水添MDI: 4,4’-メチレン-ビス(シクロヘキシルイソシアネート)
・PTMG1000: 数平均分子量約1000のポリテトラメチレングリコール
・DEG: ジエチレングリコール
・MOCA: 3,3’-ジクロロ-4,4’-ジアミノジフェニルメタン
・3官能PPG3000: 数平均分子量3000で3官能のポリプロピレングリコール
s値とは、上述したように、ポリアミン化合物のアミノ基(D)と、前記イソシアネート基含有化合物(A)とは別に用意した前記ポリオール化合物(C-2)の水酸基との当量の和(活性水素基の当量)に対する前記ポリアミン化合物(D)のアミノ基の当量比(アミノ基/(アミノ基+水酸基))を示す数値である。
比較例1において、従来知られている硬質(乾式)研磨パッドを製造した。第1成分のプレポリマとして2,4-TDIの316部、水添MDIの88部、数平均分子量約1000のPTMGの539部を反応させた後、ジエチレングリコールの57部を加えて更に反応させたイソシアネート含有量が9.0%、NCO当量466のイソシアネート基含有ウレタンプレポリマを用いこれを55℃に加熱し減圧下で脱泡した。第2成分の鎖伸長剤としての固形MOCAを120℃で溶融し、減圧下で脱泡した。第3成分として発泡剤(Expancel551DE)を2重量%となるように第1成分に混合し、第1成分:第2成分を重量比で1000部:256部の割合で混合機に供給した。
得られた混合液を50℃に加熱した890×890mmの型枠に注型し、100℃で5時間加熱して硬化させた後、形成されたポリウレタン樹脂発泡体を型枠から抜き出した。更にこの発泡体を厚さ1.25mmにスライスしてウレタンシートを作製し、研磨パッドを得た。
次に、固形MOCAを用い、各成分の割合を表1に示すように変動させて、密度の大きさが異なる種々の研磨パッドを製造した。
実施例1では、第1成分のプレポリマとして2,4-TDI(286部)、数平均分子量約1000のPTMG(714部)を反応させたイソシアネート含有量が7.8%、NCO当量が540のイソシアネート基含有ウレタンプレポリマを用いこれを55℃に加熱し減圧下で脱泡した。第2成分の鎖伸長剤として固形MOCAを用いこれを120℃で溶融し、減圧下で脱泡した。第3成分の水分散液は、数平均分子量3000で3官能のPPG(42部)、水(3部)、触媒(トヨキャットET、東ソー株式会社製)(1部)、シリコーン系界面活性剤(SH-193、ダウコーニング社製)(1部)をそれぞれ添加し35℃で1時間攪拌混合した後、減圧下で脱泡した。第1成分:第2成分:第3成分を重量比で1000部:168部:47部の割合で混合機に80kg/minの流量で供給した。このとき、混合機の攪拌ローターに設けられたノズルより、空気を18.2L/minの流量で供給した(すなわち、前記第1~第3成分の合計80kgあたり18.2Lの空気を供給した)。得られた混合液を型枠(890×890mm)に注型し、100℃で5時間かけて硬化させた後、形成されたポリウレタン樹脂発泡体を型枠から抜き出した。この発泡体を厚さ1.35mmにスライスしてウレタンシートを作製し、研磨パッドを得た。
混合機内に供給する各成分の割合を表1のように変更した以外は実施例1と同様の方法により、厚さ1.32~1.35mmの研磨パッドを得た。
次に、液状MOCAを用い、各成分の割合を表2に示すように変動させて、密度の大きさが異なる種々の研磨層を製造した。
実施例5では、第1成分のプレポリマとして2,4-TDI(286部)、数平均分子量約1000のPTMG(714部)を反応させたイソシアネート含有量が7.8%、NCO当量540のイソシアネート基含有ウレタンプレポリマを用いこれを55℃に加熱し減圧下で脱泡した。第2成分の鎖伸長剤として、液状MOCA(234部)を減圧下で脱泡した。第3成分の水分散液は、数平均分子量3000で3官能のPPG(41部)、水(3部)、触媒(トヨキャットET、東ソー株式会社製)(1部)、シリコーン系界面活性剤(SH-193、ダウコーニング社製)(4部)をそれぞれ添加し攪拌混合した後、減圧下で脱泡した。第1成分:第2成分:第3成分を重量比で1000部:234部:49部の割合で混合機に80kg/minの流量で供給した。このとき、混合機内に攪拌ローターに設けられたノズルより、空気を19.1L/minの流量で供給した(すなわち、前記第1~第3成分の合計80kgあたり19.1Lの空気を供給した)。得られた混合液を型枠に注型し、100℃で5時間かけて硬化させた後、形成されたポリウレタン樹脂発泡体を型枠から抜き出した。この発泡体を厚さ1.28mmにスライスしてウレタンシートを作製し、研磨パッドを得た。
混合機内に供給する各成分の割合を表2のように変更したこと以外は実施例5と同様の方法により、厚さ1.28~1.30mmの研磨パッドを得た。
最後に、ポリイソシアネート化合物、ポリオール化合物及びポリアミン化合物の量を増減させて研磨層を製造した。
実施例10では、第1成分のプレポリマとして2,4-TDI(325部)、数平均分子量約1000のPTMG(675部)を反応させたイソシアネート含有量が10.0%、NCO当量420のイソシアネート基含有ウレタンプレポリマを用いこれを55℃に加熱し減圧下で脱泡した。第2成分の鎖伸長剤として、液状MOCA(397部)を減圧下で脱泡した。第3成分の水分散液は、数平均分子量3000で3官能のPPG(43部)、水(1部)、触媒(トヨキャットET、東ソー株式会社製)(1部)、シリコーン系界面活性剤(SH-193、ダウコーニング社製)(4部)をそれぞれ添加し攪拌混合した後、減圧下で脱泡した。第1成分:第2成分:第3成分を重量比で1000部:397部:49部の割合で80kg/minの流量で混合機に供給した。このとき、混合機内に空気を19.1L/minの流量で供給した。得られた混合液を型枠に注型し硬化させた後、形成されたポリウレタン樹脂発泡体を型枠から抜き出した。この発泡体を厚さ1.27mmにスライスしてウレタンシートを作製し、研磨パッドを得た。
実施例11~15及び比較例9~18について、各成分の割合を表3~4に示すとおりに変更した以外は実施例10と同様の方法により、厚さ1.27~1.30mmの研磨パッドを製造した。
上記の各実施例及び比較例について、ウレタンシートのヤング率(kPa)、密度(g/cm3)、Z値、ハードセグメント含有率(%)、A硬度(°)、D硬度(°)、平均気泡径(μm)、1mm2当たりの気泡個数、貯蔵弾性率E’40(Mpa)、及び厚み(mm)を算出又は測定した。その結果を表1~4に示す。
なお、各項目の測定方法は以下の通りである。
各実施例及び比較例の研磨パッドについて、以下の研磨条件で研磨加工を行い、研磨レート、研磨均一性及びスクラッチの有無を測定した。被研磨物としては、12インチのシリコンウェハ上にテトラエトキシシランをCVDで絶縁膜を1μmの厚さになるように形成した基板(均一性(CV%)が13%)を用いた。
研磨レートは、1分間あたりの研磨量を厚さ(nm)で表したものであり、研磨加工前後の基板の絶縁膜について各々17箇所の厚み測定結果から平均値を求めた。なお、厚み測定は、光学式膜厚膜質測定器(KLAテンコール社製、ASET-F5x)のDBSモードにて測定した。
研磨均一性は、前記の17箇所の厚み測定結果のバラツキ(標準偏差÷平均値)から求めた。
スクラッチの評価では、25枚の基板を繰り返し3回順次研磨し、研磨加工後の21~25枚目の基板5枚について、パターンなしウェハ表面検査装置(KLAテンコール社製、Surfscan SP1DLS)の高感度測定モードにて測定し、基板表面におけるスクラッチの有無を評価した。
・使用研磨機:荏原製作所社製、F-REX300。
・回転数:(定盤)70rpm、(トップリング)71rpm。
・研磨圧力:220hPa。
・研磨剤:キャボット社製、品番:SS25(SS25原液:純水=1:1の混合液を使用)。
・研磨剤温度:30℃。
・研磨剤吐出量:200ml/min。
・使用ワーク(被研磨物):12インチφシリコンウェハ上にテトラエトキシシランをCVDで絶縁膜1μmの厚さになるように形成した基板。
・研磨時間:60秒間/各回。
・ドレッシング:(研磨布貼付後)10min。
ここで、本発明の研磨パッドは、研磨レート、研磨均一性及びスクラッチ抑制が、バランスよく効果として発揮されていることを要するものであるため、商品価値上、以下のようにして研磨試験の結果を評価した。
研磨レートは200以上(nm/min)を○、190以上~200未満(nm/min)を△、190未満(nm/min)を×として評価した。
研磨均一性は、7.0以下(CV%)を○、7.0超過~8.0以下(CV%)を△、8.0超過(CV%)を×として評価した。
スクラッチの有無は、無(0枚)を○、有(1枚以上)を×として評価した。
そして、研磨レート、研磨均一性及びスクラッチの有無の3種について、△が0~1つのもの(3種全てが○のもの及び2種が○で1種が△のもの)を好ましい例(実施例)とし、△を2つ以上有するサンプル及び×を1つでも有するサンプルを、本発明において好ましくない例(比較例)として評価した。
空気を吹き込まず、水分散液も用いない比較例1により製造された従来の研磨パッドは、密度、縦弾性係数ともに高かった。また、1mm2当たりの気泡の個数が多く、平均気泡径が小さい構造、すなわち、非常に小さな気泡が無数に存在する構造を有していた(図1の右図参照)。その結果、スクラッチが発生し、研磨均一性の点でも満足のいく数値は得られなかった。
鎖伸長剤として固形MOCAを用いた実施例1~4及び比較例2~5において、水の添加量が多く固形MOCAの量が少ない場合には密度が小さくなりすぎ、研磨レート及び研磨均一性の点で劣る結果となった(比較例2)。逆に、水の添加量が少なく固形MOCAの量が多い場合には、縦弾性係数が大きくなりすぎ、密度が大きくなるために、スクラッチが発生し、研磨均一性の点でも十分な結果は得られなかった(比較例3~5)。
一方、密度及び縦弾性係数が本発明の範囲内となるように固形MOCA及び水添加量を調整して製造された研磨パッドでは、スクラッチが発生せず、研磨レート、研磨均一性のいずれにおいても良好な結果が得られた(実施例1~4)。
鎖伸長剤として液体MOCAを用いた実施例5~9及び比較例6~8において、水の添加量が多く液状MOCAの量が少ない場合には密度が小さくなりすぎ、縦弾性係数も小さくなってしまうために、特に研磨レート、研磨均一性の点で十分な結果は得られなかった(比較例6)。逆に、水の添加量が少なく液状MOCAの量が多い場合には、縦弾性係数が大きくなりすぎ、密度が大きくなるため、スクラッチが発生し、研磨均一性の点でも劣る結果となった(比較例7~8)。
一方、密度及び縦弾性係数が本発明の範囲内となるように液状MOCA及び水添加量を調整して製造された研磨パッドでは、スクラッチが発生せず、研磨レート、研磨均一性のいずれにおいても良好な結果が得られた(実施例5~9)。
ポリイソシアネート化合物、ポリオール化合物及びポリアミン化合物の含有比率を変動させた実施例10~15及び比較例9~13において、ポリアミン化合物の量がポリオール化合物の量に対して多すぎる場合(当量比)には、縦弾性係数が大きくなりすぎてしまい、スクラッチの発生、低研磨レート及び低研磨均一性を2種以上生ずる結果となった(比較例9~10)。
逆に、ポリアミン化合物の量がポリオール化合物の量に対して少なすぎる場合(当量比)には、縦弾性係数が小さくなりすぎてしまい、特に研磨均一性や研磨レートの点で大きく劣る結果となった(比較例11~13)。
一方、ポリアミン化合物のアミノ基とプレポリマ形成用のポリオール化合物の水酸基との当量比を、縦弾性係数及び密度が本発明の範囲内になるように調整して製造された研磨パッドでは、スクラッチが発生せず、研磨レート、研磨均一性のいずれも十分良好な結果が得られた(実施例10~15)。
Claims (12)
- 略球状の気泡を含むポリウレタンポリウレア樹脂発泡体を有する研磨層を備える研磨パッドであって、
前記ポリウレタンポリウレア樹脂発泡体の縦弾性係数Eが450~30000kPaの範囲内であり、且つ、前記ポリウレタンポリウレア樹脂発泡体の密度Dが0.30~0.60g/cm3の範囲内であることを特徴とする、半導体デバイス研磨用の研磨パッド。 - 前記ポリウレタンポリウレア樹脂発泡体の、Z=100×HSC+5000×D-5×dで求められるZ値が3300~5000の範囲内であることを特徴とする、請求項1に記載の研磨パッド。
(式中、Dは密度(g/cm3)を表し、dは平均気泡径(μm)を表し、HSCは下記式(1)により求められるハードセグメント含有率である:
HSC=100×(r-1)×(Mdi+Mda)÷(Mg+r×Mdi+(r-1)×Mda) ・・・(1)
式(1)中、Mdiは前記ポリウレタンポリウレア樹脂を構成するポリイソシアネート化合物のイソシアネート基2官能あたりの平均分子量を表し;Mgは前記ポリウレタンポリウレア樹脂を構成するポリオール化合物の水酸基2官能あたりの平均分子量を表し;Mdaは前記ポリウレタンポリウレア樹脂を構成するポリアミン化合物のアミノ基2官能あたりの平均分子量を表し;rは前記ポリウレタンポリウレア樹脂を構成するポリオール化合物の水酸基に対するポリイソシアネート化合物のイソシアネート基の当量比を表す。) - 前記ポリウレタンポリウレア樹脂発泡体の平均気泡径が120~185μmである、請求項1又は2に記載の研磨パッド。
- 前記ポリウレタンポリウレア樹脂発泡体のA硬度が20~55度である、請求項1~3のいずれか一項に記載の研磨パッド。
- 前記ポリウレタンポリウレア樹脂発泡体のD硬度が5~35度である、請求項1~4のいずれか一項に記載の研磨パッド。
- 前記ポリウレタンポリウレア樹脂発泡体の40℃、初期荷重10g、歪範囲0.01~4%、測定周波数0.2Hz、引っ張りモードにおける貯蔵弾性率E’が1~30MPaである、請求項1~5のいずれか一項に記載の研磨パッド。
- 前記研磨層の研磨面と反対の面側に前記研磨層よりも硬い層が張り合わされていることを特徴とする、請求項1~6のいずれか一項に記載の研磨パッド。
- イソシアネート基含有化合物(A)と、ポリイソシアネート化合物(B)と、ポリアミン化合物(D)と、水、整泡剤及び反応触媒を含む混合液(E)と、各成分に対して非反応性の気体とを準備する準備工程;
少なくとも、前記イソシアネート基含有化合物(A)と、ポリイソシアネート化合物(B)と、ポリアミン化合物(D)と、水、整泡剤及び反応触媒を含む混合液(E)と、各成分に対して非反応性の気体とを混合して発泡体成形用混合液を得る混合工程;
前記発泡体成形用混合液からポリウレタンポリウレア樹脂発泡体を成形する発泡体成形工程;及び
前記ポリウレタンポリウレア樹脂発泡体から、被研磨物を研磨加工するための研磨面を有する研磨層を形成する研磨層形成工程、を有することを特徴とする、請求項1~7のいずれか一項に記載の研磨パッドの製造方法。 - 前記準備工程において、更にポリオール化合物(C-2)を準備し、前記混合工程で混合することを特徴とする、請求項8に記載の研磨パッドの製造方法。
- 前記準備工程において、前記ポリアミン化合物(D)のアミノ基と前記ポリオール化合物(C-2)の水酸基との当量の和(活性水素基の当量)に対する前記ポリアミン化合物(D)のアミノ基の当量比が、0.70~0.97(アミノ基/(アミノ基+水酸基))となるように準備されることを特徴とする、請求項9に記載の研磨パッドの製造方法。
- 前記ポリアミン化合物(D)が、メチレンビス-o-クロロアニリン(MOCA)の単量体と多量体の混合物であって該多量体を15質量%以上含有する粗製MOCAであることを特徴とする、請求項8~10のいずれか1項に記載の研磨パッドの製造方法。
- 前記ポリオール化合物(C-2)が、数平均分子量500~5000のポリテトラメチレングリコールもしくはポリプロピレングリコール又はこれらの混合物であることを特徴とする、請求項9又は10に記載の研磨パッドの製造方法。
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EP2886249A1 (en) * | 2013-12-17 | 2015-06-24 | Fujibo Holdings, Inc. | Resin lapping plate and lapping method using the same |
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Publication number | Priority date | Publication date | Assignee | Title |
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US8702479B2 (en) | 2010-10-15 | 2014-04-22 | Nexplanar Corporation | Polishing pad with multi-modal distribution of pore diameters |
JP6116487B2 (ja) * | 2011-02-24 | 2017-04-19 | スリーエム イノベイティブ プロパティズ カンパニー | フォーム裏材を含むコーティングされた研磨物品、及びその製造方法 |
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JP2015157333A (ja) * | 2014-02-24 | 2015-09-03 | ニッタ・ハース株式会社 | 研磨パッド |
US10946495B2 (en) | 2015-01-30 | 2021-03-16 | Cmc Materials, Inc. | Low density polishing pad |
US10813444B2 (en) * | 2018-05-16 | 2020-10-27 | Jh Rhodes Company, Inc. | Porous polymeric polishing bristles and methods for their manufacture |
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EP4240782A1 (en) * | 2020-11-05 | 2023-09-13 | Huntsman International LLC | Reactive formulations for forming a strong polyurethane-polyurea comprising water blown foam |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH106211A (ja) | 1996-06-26 | 1998-01-13 | Asahi Glass Co Ltd | 研磨パッドおよび板状材の研磨方法 |
JP2006114885A (ja) | 2004-09-17 | 2006-04-27 | Jsr Corp | 化学機械研磨パッド及び化学機械研磨方法 |
JP3788729B2 (ja) | 2000-08-23 | 2006-06-21 | 東洋ゴム工業株式会社 | 研磨パッド |
JP3924952B2 (ja) | 1998-10-13 | 2007-06-06 | 東レ株式会社 | 研磨装置および研磨パッド |
JP3983610B2 (ja) | 2002-07-02 | 2007-09-26 | 株式会社クラレ | 熱可塑性ポリウレタン発泡体およびそれからなる研磨パッド |
JP2009214275A (ja) * | 2008-03-12 | 2009-09-24 | Toyo Tire & Rubber Co Ltd | 研磨パッド |
JP4338150B2 (ja) | 2003-10-17 | 2009-10-07 | 東レ株式会社 | 発泡ポリウレタンおよびその製造方法 |
JP2009241224A (ja) * | 2008-03-31 | 2009-10-22 | Toyo Tire & Rubber Co Ltd | 研磨パッド作製用積層シート |
JP2009256473A (ja) | 2008-04-17 | 2009-11-05 | Nitta Haas Inc | 発泡ポリウレタンの製造方法および研磨パッド |
JP2010058194A (ja) | 2008-09-02 | 2010-03-18 | Fujibo Holdings Inc | 研磨パッドの製造方法 |
JP2010076076A (ja) * | 2008-09-29 | 2010-04-08 | Fujibo Holdings Inc | 研磨加工用の研磨パッドに用いられる研磨シートおよび研磨パッド |
JP2010082721A (ja) * | 2008-09-30 | 2010-04-15 | Fujibo Holdings Inc | 研磨パッド |
JP2010082708A (ja) * | 2008-09-29 | 2010-04-15 | Fujibo Holdings Inc | 研磨パッド |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5104424A (en) * | 1989-11-20 | 1992-04-14 | Norton Company | Abrasive article |
JP3890786B2 (ja) * | 1998-11-09 | 2007-03-07 | 東レ株式会社 | 研磨装置および研磨パッド |
WO2002043921A1 (fr) * | 2000-12-01 | 2002-06-06 | Toyo Boseki Kabushiki Kaisha | Tampon de polissage, procede de fabrication de ce tampon de polissage, et couche d'amortissement pour ce tampon de polissage |
US6612917B2 (en) * | 2001-02-07 | 2003-09-02 | 3M Innovative Properties Company | Abrasive article suitable for modifying a semiconductor wafer |
JP4686912B2 (ja) * | 2001-06-15 | 2011-05-25 | 東レ株式会社 | 研磨パッド |
JP2003062748A (ja) * | 2001-08-24 | 2003-03-05 | Inoac Corp | 研磨用パッド |
JP3325562B1 (ja) | 2001-12-07 | 2002-09-17 | 東洋ゴム工業株式会社 | 発泡ポリウレタン研磨パッドの製造方法 |
JP4555559B2 (ja) * | 2003-11-25 | 2010-10-06 | 富士紡ホールディングス株式会社 | 研磨布及び研磨布の製造方法 |
KR20070057157A (ko) | 2004-08-25 | 2007-06-04 | 제이.에이치.로데스 컴퍼니, 인코퍼레이티드 | 연마 패드 및 패드 제거 속도와 평탄화의 개선 방법 |
US20060089095A1 (en) * | 2004-10-27 | 2006-04-27 | Swisher Robert G | Polyurethane urea polishing pad |
JP4964420B2 (ja) * | 2005-02-21 | 2012-06-27 | 東洋ゴム工業株式会社 | 研磨パッド |
JP2006245445A (ja) | 2005-03-07 | 2006-09-14 | Nihon Micro Coating Co Ltd | 研磨パッド |
CN101724167B (zh) * | 2005-07-15 | 2013-06-26 | 东洋橡胶工业株式会社 | 层叠片及其制造方法 |
JP2007181913A (ja) * | 2005-12-05 | 2007-07-19 | Toray Ind Inc | 研磨パッド |
JP2007238783A (ja) | 2006-03-09 | 2007-09-20 | Mitsui Chemicals Inc | 発泡体 |
CN101966697B (zh) * | 2006-04-19 | 2015-04-22 | 东洋橡胶工业株式会社 | 抛光垫的制造方法 |
WO2008029538A1 (fr) * | 2006-09-08 | 2008-03-13 | Toyo Tire & Rubber Co., Ltd. | Tampon à polir |
US7371160B1 (en) * | 2006-12-21 | 2008-05-13 | Rohm And Haas Electronic Materials Cmp Holdings Inc. | Elastomer-modified chemical mechanical polishing pad |
SG177964A1 (en) * | 2007-01-15 | 2012-02-28 | Toyo Tire & Rubber Co | Polishing pad and method for producing the same |
JP4943233B2 (ja) * | 2007-05-31 | 2012-05-30 | 東洋ゴム工業株式会社 | 研磨パッドの製造方法 |
US8449357B2 (en) * | 2007-10-05 | 2013-05-28 | Chien-Min Sung | Polymeric fiber CMP pad and associated methods |
JP4593643B2 (ja) * | 2008-03-12 | 2010-12-08 | 東洋ゴム工業株式会社 | 研磨パッド |
JP5242322B2 (ja) | 2008-09-30 | 2013-07-24 | 富士紡ホールディングス株式会社 | 研磨パッドおよびその製造方法 |
JP5846714B2 (ja) | 2009-04-06 | 2016-01-20 | ニッタ・ハース株式会社 | 研磨パッド |
JP5868566B2 (ja) | 2009-05-28 | 2016-02-24 | ニッタ・ハース株式会社 | 研磨パッド |
JP5184448B2 (ja) * | 2009-06-23 | 2013-04-17 | 富士紡ホールディングス株式会社 | 研磨パッド、その製造方法および研磨加工方法 |
-
2011
- 2011-04-15 JP JP2011091283A patent/JP5687118B2/ja active Active
-
2012
- 2012-04-16 EP EP12772052.2A patent/EP2698811B1/en active Active
- 2012-04-16 SG SG2013076708A patent/SG194190A1/en unknown
- 2012-04-16 US US14/111,962 patent/US9011212B2/en active Active
- 2012-04-16 CN CN201280028623.9A patent/CN103608903A/zh active Pending
- 2012-04-16 WO PCT/JP2012/060273 patent/WO2012141327A1/ja active Application Filing
- 2012-04-16 KR KR1020137029915A patent/KR101889123B1/ko active IP Right Grant
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH106211A (ja) | 1996-06-26 | 1998-01-13 | Asahi Glass Co Ltd | 研磨パッドおよび板状材の研磨方法 |
JP3924952B2 (ja) | 1998-10-13 | 2007-06-06 | 東レ株式会社 | 研磨装置および研磨パッド |
JP3788729B2 (ja) | 2000-08-23 | 2006-06-21 | 東洋ゴム工業株式会社 | 研磨パッド |
JP3983610B2 (ja) | 2002-07-02 | 2007-09-26 | 株式会社クラレ | 熱可塑性ポリウレタン発泡体およびそれからなる研磨パッド |
JP4338150B2 (ja) | 2003-10-17 | 2009-10-07 | 東レ株式会社 | 発泡ポリウレタンおよびその製造方法 |
JP2006114885A (ja) | 2004-09-17 | 2006-04-27 | Jsr Corp | 化学機械研磨パッド及び化学機械研磨方法 |
JP2009214275A (ja) * | 2008-03-12 | 2009-09-24 | Toyo Tire & Rubber Co Ltd | 研磨パッド |
JP2009241224A (ja) * | 2008-03-31 | 2009-10-22 | Toyo Tire & Rubber Co Ltd | 研磨パッド作製用積層シート |
JP2009256473A (ja) | 2008-04-17 | 2009-11-05 | Nitta Haas Inc | 発泡ポリウレタンの製造方法および研磨パッド |
JP2010058194A (ja) | 2008-09-02 | 2010-03-18 | Fujibo Holdings Inc | 研磨パッドの製造方法 |
JP2010076076A (ja) * | 2008-09-29 | 2010-04-08 | Fujibo Holdings Inc | 研磨加工用の研磨パッドに用いられる研磨シートおよび研磨パッド |
JP2010082708A (ja) * | 2008-09-29 | 2010-04-15 | Fujibo Holdings Inc | 研磨パッド |
JP2010082721A (ja) * | 2008-09-30 | 2010-04-15 | Fujibo Holdings Inc | 研磨パッド |
Non-Patent Citations (1)
Title |
---|
P. J. FLORY, JOURNAL OF AMERICAN CHEMICAL SOCIETY, vol. 58, 1936, pages 1877 - 1885 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3006220A1 (fr) * | 2013-05-31 | 2014-12-05 | Rohm & Haas Elect Mat | Empilement formant tampon de polissage chimique mecanique multicouche avec une couche de polissage souple et conditionnable |
EP2886249A1 (en) * | 2013-12-17 | 2015-06-24 | Fujibo Holdings, Inc. | Resin lapping plate and lapping method using the same |
US20160001417A1 (en) * | 2014-07-07 | 2016-01-07 | Jh Rhodes Company, Inc. | Polishing material for polishing hard surfaces, media including the material, and methods of forming and using same |
US9649741B2 (en) * | 2014-07-07 | 2017-05-16 | Jh Rhodes Company, Inc. | Polishing material for polishing hard surfaces, media including the material, and methods of forming and using same |
Also Published As
Publication number | Publication date |
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JP2012223833A (ja) | 2012-11-15 |
EP2698811B1 (en) | 2019-08-14 |
KR101889123B1 (ko) | 2018-08-16 |
EP2698811A4 (en) | 2014-10-01 |
US20140106652A1 (en) | 2014-04-17 |
US9011212B2 (en) | 2015-04-21 |
EP2698811A1 (en) | 2014-02-19 |
CN103608903A (zh) | 2014-02-26 |
JP5687118B2 (ja) | 2015-03-18 |
SG194190A1 (en) | 2013-11-29 |
KR20140035375A (ko) | 2014-03-21 |
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