CN114536212B - Microporous thermoplastic polyurethane polishing pad and semi-continuous preparation method thereof - Google Patents
Microporous thermoplastic polyurethane polishing pad and semi-continuous preparation method thereof Download PDFInfo
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- CN114536212B CN114536212B CN202210110517.0A CN202210110517A CN114536212B CN 114536212 B CN114536212 B CN 114536212B CN 202210110517 A CN202210110517 A CN 202210110517A CN 114536212 B CN114536212 B CN 114536212B
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 97
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 97
- 238000005498 polishing Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 53
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012530 fluid Substances 0.000 claims abstract description 35
- 238000005187 foaming Methods 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 238000003490 calendering Methods 0.000 claims abstract description 6
- 239000003292 glue Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000004080 punching Methods 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 15
- 238000010924 continuous production Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 28
- 235000012431 wafers Nutrition 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010437 gem Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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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
-
- 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
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
- B24D18/0027—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for by impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
- B24D18/0072—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for using adhesives for bonding abrasive particles or grinding elements to a support, e.g. by gluing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
- B24D18/009—Tools not otherwise provided for
-
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention discloses a microporous thermoplastic polyurethane polishing pad and a semi-continuous preparation method thereof, and relates to the technical field of integrated circuit materials. The semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad comprises the following steps: (1) Melt extrusion, calendaring and rolling of high-hardness thermoplastic polyurethane and an auxiliary agent; (2) Immersing the coiled material in high-pressure fluid, locking gas at low temperature, storing at low temperature, heating, foaming and rolling to obtain a foaming coiled material; (3) peeling and punching the foaming coiled material to obtain an upper layer pad; (4) Grinding the upper layer pad, grooving, attaching back glue or attaching a buffer layer and back glue to obtain a microporous thermoplastic polyurethane polishing pad; the hardness of the high-hardness thermoplastic polyurethane is 55-85 HD; the hardness of the upper layer pad is 25-80 HD, the thickness is 1.3-2.0 mm, and the density is 0.1-1.0 g/cm 3 The size of the foam holes is 1-200 mu m; the high-pressure fluid is two fluids of carbon dioxide and nitrogen. The polishing pad prepared by the method of the invention has excellent polishing effect and polishing rate.
Description
Technical Field
The invention relates to the technical field of integrated circuit materials, in particular to a microporous thermoplastic polyurethane polishing pad and a semi-continuous preparation method thereof.
Background
Chemical-mechanical polishing (CMP) processes are used for surface planarization of semiconductor devices, precious stones, glass, and the like. Planarization is required, for example, in the fabrication of semiconductor devices, where various process layers are typically formed on a wafer, after selective removal or patterning of portions of the layers, and where a further process layer is deposited on the wafer. The CMP polishing process requires a polishing pad and a polishing liquid. In a typical CMP process, a wafer carrier is mounted on a carrier in a CMP tool, a force is applied to the carrier and wafer to press against a polishing pad, the carrier and wafer are rotated on a CMP tool polishing table, a polishing liquid is introduced between the wafer and the polishing pad during polishing, and a portion of the layer of polishing material is removed under chemical and mechanical forces. Since the process layer may comprise an insulating layer, a gate oxide layer, a conductive layer, a metal or glass layer, etc., the polishing pad and the polishing liquid need to cooperate to uniformly remove different materials in the layer, the same or similar removal rates result in a planarized working layer, and the different removal rates result in defects in the working layer. As integrated circuit feature sizes decrease, CMP-induced defects are amplified.
Porous polyurethanes have proven to be a class of materials that produce high performance polishing pads with consistently reproducible polishing characteristics. The prior art of porous polyurethane materials is to pour a polyurethane foaming stock solution into a porous cake and cut the porous cake into polishing pads of several thicknesses. The polyurethane foaming stock solution generates a large amount of heat in the foaming process, and the heat is prevented from dissipating due to heat insulation of the foaming structure, so that a porous polyurethane core layer has a macroporous structure and wide cell size distribution, and the performance consistency of the microporous polyurethane polishing pad is affected; meanwhile, most of casting molds are of disc structures, the processing mode is intermittent and low-efficiency, and continuous porous polyurethane sheets are difficult to prepare. Therefore, there is a need to provide a method for preparing a porous polyurethane sheet with simple processing and good processing effect.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned disadvantages of the prior art and to provide a microporous thermoplastic polyurethane polishing pad and a semi-continuous production method thereof, which can efficiently produce a polishing pad, and which can produce a polishing pad having excellent polishing efficiency and polishing effect.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a semi-continuous process for preparing a microporous thermoplastic polyurethane polishing pad, the process comprising:
(1) Drying, premixing, twin-screw continuous extrusion, calendaring and rolling the high-hardness thermoplastic polyurethane and the auxiliary agent to obtain a precursor high-hardness thermoplastic polyurethane coiled material;
(2) Impregnating the precursor high-hardness thermoplastic polyurethane coiled material with high-pressure fluid, locking gas at low temperature, storing at low temperature, heating for foaming, and continuously rolling to obtain a high-hardness thermoplastic polyurethane foaming coiled material;
(3) Peeling and continuously punching the high-hardness thermoplastic polyurethane foaming coiled material to obtain an upper layer pad;
(4) Grinding the upper layer pad, grooving, attaching back glue or attaching a buffer layer and back glue to obtain a microporous thermoplastic polyurethane polishing pad;
the hardness of the high-hardness thermoplastic polyurethane is 55-85 HD; the hardness of the upper layer pad is 25-80 HD, the thickness is 1.3-2.0 mm, and the density is 0.1-1.0 g/cm 3 The average cell size is 1-200 mu m;
the high-pressure fluid is two fluids of carbon dioxide and nitrogen.
The invention selects the thermoplastic polyurethane with the hardness of 55-90 HD to prepare the polishing pad, which can ensure that the polishing pad has enough hardness to remove the oxide layer on the surface of the wafer and has certain removal efficiency; the precursor high-hardness thermoplastic polyurethane is impregnated by two high-pressure fluids, namely carbon dioxide and nitrogen, so that the upper layer pad is smoother, the cell structure is more uniform, the polishing pad has a good polishing effect, and scratches are less generated on the surface of a polished object.
Preferably, in the step (2), the impregnation process is performed in two steps, namely, injecting 2-10 MPa of carbon dioxide fluid and then injecting 0.1-5 MPa of nitrogen fluid.
The carbon dioxide fluid diffuses faster in the thermoplastic polyurethane coiled material, has higher solubility, is favorable for preparing the low-density thermoplastic polyurethane foaming coiled material, but has high desorption speed in the foaming process of the thermoplastic polyurethane coiled material, and easily causes the phenomena of macropores and uneven cell sizes on the surface of the thermoplastic polyurethane foaming coiled material, and obvious volume shrinkage and product surface wrinkling. The nitrogen fluid has relatively small solubility in the thermoplastic polyurethane coiled material and low diffusion coefficient, and is easy to increase the density of the thermoplastic polyurethane foaming coiled material, but has excellent surface quality. The inventor of the application confirms through a large number of experiments that the thermoplastic polyurethane coiled material is subjected to dipping treatment by using the carbon dioxide fluid and the nitrogen fluid, so that the thermoplastic polyurethane foaming coiled material with low density, high surface flatness and uniform cell structure can be prepared, and the polishing pad prepared from the foaming coiled material has good polishing efficiency and polishing effect.
Further preferably, in the impregnation process, 3-8 MPa of carbon dioxide fluid is injected first, and then 0.5-4 MPa of nitrogen fluid is injected. Controlling the pressure of both within the above range can further improve the overall performance of the polishing pad.
Preferably, in the step (2), the mass content of the high-pressure fluid in the impregnated thermoplastic polyurethane coiled material obtained after the impregnation is 1-10%.
The content (%) = (m) of the high-pressure fluid in the high-hardness thermoplastic polyurethane coiled material 1 -m 0 )×100％/m 0 The method comprises the steps of carrying out a first treatment on the surface of the Wherein m is 0 Is the mass, m of the precursor high-hardness thermoplastic polyurethane coiled material 1 The mass of the impregnated high-hardness thermoplastic polyurethane coiled material is that after the high-pressure fluid is impregnated, the high-hardness thermoplastic polyurethane coiled material is desorbed for 10min at normal temperature and normal pressure. By optimizing the impregnation content of the high pressure fluid, the density, cell size, cell density, etc. properties of the subsequent product can be further controlled.
Preferably, in the step (1), the extrusion temperature is: 190-220 ℃ and the die head temperature of the extruder is 210-220 ℃; the calendaring roller is cooled by 5-15 ℃ cooling water.
Preferably, in the step (2), the air is blocked at a low temperature of between 18 ℃ below zero and 0 ℃, then the air is stored at a low temperature of between 18 ℃ below zero and 15 ℃, and then a heating medium is introduced to perform physical foaming. The high-hardness thermoplastic polyurethane of the invention has vitrification at-20 to-50 ℃, so that the movement escape of high-pressure fluid can be limited when the temperature is maintained within the above preferred range.
Preferably, the thickness of the precursor high-hardness thermoplastic polyurethane coiled material is 1-3 mm; the thickness of the high-hardness thermoplastic polyurethane foaming coiled material is 2-5 mm, and the density is 0.1-1.0 g/cm 3 The average cell size is 1 to 200 μm and the hardness is 20 to 80HD. For the high-hardness thermoplastic polyurethane, the extrusion processing process is difficult, the coiled material with high thickness is difficult to prepare, and the coiled material with the thickness exceeding 3mm has relatively high flatnessAnd when the thickness of the precursor high-hardness thermoplastic polyurethane coiled material is less than 1mm, the later foaming effect is poor.
Preferably, when the thickness of the high-hardness thermoplastic polyurethane foaming coiled material is 2-3 mm, an upper cushion with a uniform cell structure on one side and a non-foaming skin structure on the other side is obtained after continuous slitting and peeling; when the thickness of the high-hardness thermoplastic polyurethane foaming coiled material is 3.1-4 mm, obtaining an upper cushion with uniform cell structures on both sides through continuous cutting and peeling; when the thickness of the high-hardness thermoplastic polyurethane coiled material obtained in the step (3) is 4.1-5.0mm, continuously slitting and peeling, and obtaining the upper cushion with two rolls and one surface having a uniform cell structure after slitting.
Preferably, the auxiliary agent is an antioxidant and a lubricant, and the auxiliary agent accounts for 0.5-5% of the mass of the high-hardness thermoplastic polyurethane. The antioxidant can be added to improve the stability of the product, and the lubricant can be added to improve the processability of the thermoplastic polyurethane, so that the components of the prepared product are more uniform.
Meanwhile, the invention also discloses a microporous thermoplastic polyurethane polishing pad prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the invention simplifies the preparation method of the polishing pad by selecting the preparation raw materials of the upper layer pad in the polishing pad and controlling the high-pressure fluid to be carbon dioxide fluid and nitrogen fluid. The microporous thermoplastic polyurethane polishing pad can be applied to the polishing field of semiconductor wafers, precious stones and glass.
Drawings
FIG. 1 is a schematic illustration of a continuous die-cutting process for making a microporous thermoplastic polyurethane polishing pad according to the present invention;
FIG. 2 is an optical view of a high hardness thermoplastic polyurethane foam coil of the present invention;
fig. 3 is an optical view of the upper pad according to the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples.
The materials used in the examples and comparative examples are as follows:
high hardness thermoplastic polyurethane 1: lu Borun ESTANE 58133, hardness 55HD;
high hardness thermoplastic polyurethane 2: lu Borun ESTANE 58144, hardness 65HD;
high hardness thermoplastic polyurethane 3: lu Borun ESTANE ETE 75DT3 with a hardness of 75HD;
high hardness thermoplastic polyurethane 4: lu Borun Isoplast 101LGF60 ETP with a hardness of 89D
Buffer layer: are commercially available;
and (3) back adhesive: are commercially available;
and (3) a lubricant: stearic acid, commercially available;
an antioxidant: antioxidant 1010, commercially available.
Example 1
An embodiment of a semi-continuous preparation method of a microporous thermoplastic polyurethane polishing pad according to the present invention comprises the following steps:
(1) Sequentially drying, premixing, continuously extruding by a double screw, calendaring and rolling 100 parts of high-hardness thermoplastic polyurethane 1, 2 parts of lubricant and 0.5 part of antioxidant to obtain a precursor high-hardness thermoplastic polyurethane coiled material, wherein the temperature from a feeding port to a fourth temperature zone of an extruder is sequentially 199 ℃, 204 ℃, 210 ℃, 215 ℃, 216 ℃, the temperature of the extruder is controlled by circulating water at 10 ℃, the die head temperature of the extruder is 213+/-0.2 ℃, and the temperature of the extruder is independently controlled by heat conducting oil;
(2) Firstly injecting 5MPa of carbon dioxide into a precursor thermoplastic polyurethane coiled material, then injecting 3MPa of nitrogen to reach dissolution balance, then locking gas at 0 ℃, then storing for 6 hours at low temperature of 0 ℃, then using hot air to raise the temperature for foaming, and continuously rolling to obtain a high-hardness thermoplastic polyurethane foaming coiled material;
(3) Continuously cutting a high-hardness thermoplastic polyurethane foaming coiled material, peeling one side, and continuously punching to obtain a microporous thermoplastic polyurethane upper layer pad;
(4) And (3) grinding the upper layer pad flat, grooving (grooves are spiral), and attaching the buffer layer and the back adhesive to obtain the microporous thermoplastic polyurethane polishing pad.
Examples 2 to 3
Examples 2 to 3 differ from example 1 only in the type of high-hardness thermoplastic polyurethane used, respectively, as examples 2 to 3 of the semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad of the present invention.
Example 4
In one embodiment of the semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad of the present invention, the difference between the present embodiment and embodiment 1 is only that in the step (2), 3MPa of carbon dioxide is injected into the precursor thermoplastic polyurethane coiled material, and then 4MPa of nitrogen fluid is injected.
Example 5
In one embodiment of the semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad of the present invention, the difference between the present embodiment and embodiment 1 is only that in the step (2), 8MPa of carbon dioxide is injected into the precursor thermoplastic polyurethane coiled material, and then 0.5MPa of nitrogen fluid is injected.
Example 6
In one embodiment of the semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad of the present invention, the difference between the present embodiment and embodiment 1 is only that in the step (2), carbon dioxide of 2MPa is injected into the precursor thermoplastic polyurethane coiled material, and then nitrogen of 5MPa is injected.
Example 7
In one embodiment of the semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad of the present invention, the difference between the present embodiment and the embodiment 1 is only that in the step (2), 10MPa of carbon dioxide is injected into the precursor thermoplastic polyurethane coiled material, and then 0.1MPa of nitrogen is injected.
Example 8
An example of a semi-continuous process for preparing a microporous thermoplastic polyurethane polishing pad of the present invention differs from example 1 only in that double-sided skinning is performed.
Example 9
An example of a semi-continuous process for preparing a microporous thermoplastic polyurethane polishing pad of the present invention differs from example 1 only in that the polishing pad has no buffer layer.
Comparative example 1
A method of preparing a microporous thermoplastic polyurethane polishing pad, which differs from example 1 only in that only carbon dioxide is used in the high pressure fluid impregnation process, and the pressure is 10MPa.
Comparative example 2
A method for preparing a microporous thermoplastic polyurethane polishing pad, which is different from example 1 only in that the thermoplastic polyurethane used in preparing the upper layer pad is a high-hardness thermoplastic polyurethane 4.
The intermediate products and the final products of the examples and comparative examples were subjected to performance tests, in which the polishing efficiency and polishing effect of the polishing pad were measured after the polishing pad polished copper in a 12 inch wafer; the test results are shown in Table 1.
TABLE 1
As is clear from the above test results, the polishing pads of examples 1 to 9 all had good polishing rate and polishing effect, and the polishing rate was allThe number of defects is within 5 per minute@93 rpm and above 2.0psi, so that the requirements of most enterprises can be met. The high pressure fluid used in comparative example 1 was carbon dioxide, resulting in the productionThe density of the upper layer pad is extremely low, wrinkles and macropores appear on the surface of the foaming coiled material, and the polishing efficiency of the polishing pad is seriously affected; the high hardness thermoplastic polyurethane selected in comparative example 2 was too high in hardness, resulting in difficulty in extrusion, the thickness of the extruded thermoplastic polyurethane sheet was less than 0.5mm, foaming was unstable, and a polishing pad could not be produced.
In addition, as shown in the above test results, the pressure of the carbon dioxide fluid in example 6 was too low, resulting in a low mass content of the high pressure fluid, a high density of the upper layer pad, and a relatively high defect count, which resulted in easy defects during polishing, while in example 7, the opposite is true, the density of the upper layer pad was low, and the polishing rate was low.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A semi-continuous preparation method of a microporous thermoplastic polyurethane polishing pad, which is characterized by comprising the following steps:
(1) Drying, premixing, twin-screw continuous extrusion, calendaring and rolling the high-hardness thermoplastic polyurethane and the auxiliary agent to obtain a precursor high-hardness thermoplastic polyurethane coiled material;
(2) Impregnating the precursor high-hardness thermoplastic polyurethane coiled material with high-pressure fluid, locking gas at low temperature, storing at low temperature, heating for foaming, and continuously rolling to obtain a high-hardness thermoplastic polyurethane foaming coiled material;
(3) Peeling and punching the high-hardness thermoplastic polyurethane foaming coiled material to obtain an upper layer pad;
(4) Grinding the upper layer pad, grooving, attaching back glue or attaching a buffer layer and back glue to obtain a microporous thermoplastic polyurethane polishing pad;
the hardness of the high-hardness thermoplastic polyurethane is 55-85 HD; the hardness of the upper layer pad is 25-80 HD, and the thickness is 1.3-to-over2.0mm, and the density is 0.1-1.0 g/cm 3 The average cell size is 1-200 mu m;
the high-pressure fluid is two fluids of carbon dioxide and nitrogen;
in the step (2), the dipping process is carried out in two steps, namely, 3-8 MPa of carbon dioxide fluid is injected firstly, and then 0.5-4 MPa of nitrogen fluid is injected;
in the step (2), air is blocked at a low temperature of between 18 ℃ below zero and 0 ℃, then the air is stored at a low temperature of between 18 ℃ below zero and 15 ℃, and then a heating medium is introduced for physical foaming.
2. The method for semi-continuous production of a microporous thermoplastic polyurethane polishing pad according to claim 1, wherein in the step (2), the mass content of the high-pressure fluid in the impregnated thermoplastic polyurethane coiled material obtained after the impregnation is 1 to 10%.
3. The method for semi-continuous production of a microporous thermoplastic polyurethane polishing pad of claim 1 wherein in step (1), the extrusion temperature is: 190-220 ℃ and the die head temperature of the extruder is 210-220 ℃; the calendaring roller is cooled by adopting a cooling medium at the temperature of 5-15 ℃.
4. The semi-continuous process for preparing a microporous thermoplastic polyurethane polishing pad according to claim 1, wherein the thickness of the precursor high-hardness thermoplastic polyurethane web is 1 to 3mm; the thickness of the high-hardness thermoplastic polyurethane foaming coiled material is 2-5 mm, and the density is 0.1-1.0 g/cm 3 The average cell size is 1 to 200 μm and the hardness is 20 to 75HD.
5. The method for semi-continuous production of a microporous thermoplastic polyurethane polishing pad according to claim 4, wherein when the thickness of the high-hardness thermoplastic polyurethane foam roll is 2 to 3mm, an upper layer pad having a uniform cell structure on one side and a non-foaming skin structure on the other side is obtained by continuous slitting and peeling; when the thickness of the high-hardness thermoplastic polyurethane foaming coiled material is 3.1-4 mm, obtaining an upper cushion with uniform cell structures on both sides through continuous cutting and peeling; when the thickness of the high-hardness thermoplastic polyurethane coiled material obtained in the step (3) is 4.1-5.0mm, continuously slitting and peeling, and obtaining the upper cushion with two rolls and one surface having a uniform cell structure after slitting.
6. The semi-continuous preparation method of the microporous thermoplastic polyurethane polishing pad according to claim 1, wherein the auxiliary agent is an antioxidant and a lubricant, and the auxiliary agent accounts for 0.5-5% of the mass of the high-hardness thermoplastic polyurethane.
7. A microporous thermoplastic polyurethane polishing pad prepared by the method of any one of claims 1-6.
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