CN116372800B - Preparation method of vertical microporous polyurethane polishing pad - Google Patents
Preparation method of vertical microporous polyurethane polishing padInfo
- Publication number
- CN116372800B CN116372800B CN202310255218.0A CN202310255218A CN116372800B CN 116372800 B CN116372800 B CN 116372800B CN 202310255218 A CN202310255218 A CN 202310255218A CN 116372800 B CN116372800 B CN 116372800B
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- polyurethane
- polishing pad
- film
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- polyurethane polishing
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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
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
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- 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
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention relates to a preparation method of a vertical microporous polyurethane polishing pad, which comprises the following steps of coating polyurethane casting film liquid on the surface of a substrate, immersing the substrate in solidification liquid to enable the polyurethane casting film liquid on the surface of the substrate to undergo phase inversion to solidify into a film, forming vertical micropores which are regularly arranged in the surface of the film while forming the film, and then washing and drying the film to obtain the vertical microporous polyurethane polishing pad, wherein the polyurethane casting film liquid comprises, by weight, 100 parts of polyurethane resin, 2-5 parts of a surfactant and 30-80 parts of a solvent, and the polyurethane resin comprises, by weight, 100% of material synthesis, 20-30% of polyester polyol, 5-9% of MDI (diphenyl methane diisocyanate), 2-6% of polyethylene oxide, 0.02-0.03% of a blocking agent and the balance of the solvent. The polyurethane polishing pad has higher porosity, hardness and mechanical property, and meanwhile, vertical micropores in the polyurethane are uniformly distributed and regular in shape, and the surface of the polyurethane polishing pad has lower surface roughness.
Description
Technical Field
The invention relates to the technical field of polishing pads for chemical mechanical polishing, in particular to a preparation method of a vertical microporous polyurethane polishing pad.
Background
Chemical Mechanical Polishing (CMP) uses chemical reactions and mechanical polishing to achieve planarization. The polishing pad is one of important consumables for determining polishing rate and planarization ability in CMP, and a fiberboard structure having a plurality of capsule holes on the surface thereof, and has functions of storing, transporting a polishing liquid, removing processing residues, transferring mechanical load, maintaining a polishing environment, and the like during CMP. Polishing pads for CMP must have good chemical stability (corrosion resistance), hydrophilicity, and mechanical properties. Polishing pads can be generally classified into hard and soft. The hard polishing pad can better ensure the planeness of the surface of the workpiece, and the soft polishing pad can obtain a polishing surface with small processing deterioration layer and surface roughness value. The polishing pad can be divided into a polyurethane polishing pad, a non-woven polishing pad with a fluff structure and a two-layer composite polishing pad according to materials and structures.
The main component of the polyurethane polishing pad is polyurethane solidified by foaming body, the surface of the polyurethane polishing pad is of a closed unit structure with a plurality of hollow sphere micropores, the micropores play roles of collecting processing removed objects, conveying polishing liquid, guaranteeing chemical corrosion and the like in CMP, the polishing efficiency and the polishing uniformity are improved, the larger the pore size is, the stronger the transportation capacity is, but the rigidity and the density of the polishing pad are affected by the overlarge pore diameter, the polishing pad is the IC1000 type polishing pad of Rodel company in America, and the polishing pad is mostly used for rough polishing of silicon wafers. The raw material of the non-woven polishing pad is polymer cotton fiber, the most widely applied polishing pad is SubalVI of Rodel company in U.S. and the polishing pad is used for fine polishing of silicon wafers. The non-woven fabric polishing pad with the fluff structure takes non-woven fabric as a matrix, a polymer layer is arranged in the middle of the non-woven fabric polishing pad, the surface layer is of a porous fluff structure, the polishing pad has the widest application range, namely, the Politex polishing pad of Rodel company in America, and the polishing pad is mostly used for precisely polishing silicon wafers. The two-layer composite polishing pad meets the requirements of flatness and uniformity, adopts an upper-hard lower-soft two-layer composite structure, such as an IC1000/SubalVI composite structure polishing pad (an adhesive layer exists between the two layers), adopts a harder IC1000 on the upper layer, bears the mechanical and chemical actions in the CMP process, improves the material removal rate to obtain higher flatness, adopts a softer SubalVI on the bottom layer to improve the compressibility of the polishing process, is beneficial to improving the contact uniformity of the polishing pad surface and a workpiece, and ensures the uniform removal of materials.
At present, an imported material is still adopted for the polyurethane polishing pad used for rough polishing of the silicon wafer, and the domestic polyurethane polishing pad has the defects of irregular polyurethane foam structure, high surface roughness, low hardness and low strength, so that the domestic polyurethane polishing pad is difficult to stand in the manufacturing of an integrated circuit.
Disclosure of Invention
In order to overcome the defects of irregular polyurethane foam structure, high surface roughness, low hardness and low strength of the conventional polishing pad, the vertical micropore polyurethane polishing pad and the preparation method thereof are provided. The polyurethane polishing pad has higher porosity, hardness and mechanical property, and meanwhile, vertical micropores in the polyurethane are uniformly distributed and regular in shape, and the surface of the polyurethane polishing pad has lower surface roughness.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
The preparation method of the vertical micropore polyurethane polishing pad comprises the following steps:
coating polyurethane casting solution on the surface of a substrate, immersing the substrate in a coagulating solution to enable the polyurethane casting solution on the surface of the substrate to undergo phase inversion and solidify into a film, forming vertical micropores which are regularly arranged in the surface of the film while forming the film, and then washing and drying the film to obtain the vertical microporous polyurethane polishing pad;
the polyurethane film casting solution comprises the following materials, by weight, 100 parts of polyurethane resin, 2-5 parts of a surfactant and 30-80 parts of a solvent;
Wherein the polyurethane resin comprises, by weight, 20-30% of polyester polyol, 5-9% of MDI, 2-6% of polyethylene oxide, 0.02-0.03% of a blocking agent, and the balance of a solvent.
Further, the polyester polyol is formed by condensing bisphenol A type compound and adipic acid according to a molar ratio of 1 (1-2), wherein the bisphenol A type compound is one or more of malonyl tetraisopropanol ether, bisphenol A propoxy compound and bisphenol A ethoxy compound, and the structures of the bisphenol A type compound and the bisphenol A ethoxy compound are respectively as follows:
Still further, the condition of the synthetic process of the polyester polyol is that a polymerization inhibitor (such as methyl hydroquinone) accounting for 0.08 percent of the total mass of materials and an organotin catalyst accounting for 0.05 percent are added, the reaction is carried out for 1 to 2 hours at 150 to 170 ℃ under the protection of nitrogen, water is drained, and then the temperature is raised to 200 to 230 ℃ for continuous reaction until the acid value of a reaction system reaches 5 to 15mgKOH/g and the hydroxyl reaches 40 to 60mgKOH/g.
Further, the synthetic condition of the polyurethane resin is that the polyester polyol, the polyethylene oxide and a part of solvent are subjected to grafting reaction for 2-5 hours at 180-200 ℃, then cooled to 75-80 ℃, MDI is added to react until the system viscosity reaches 150000-250000cps, then cooled to 60-70 ℃, and a blocking agent is added to carry out blocking reaction for 0.5-3 hours, thus obtaining the polyurethane resin.
Further, the end capping agent is methanol, and the solvent is DMF.
Further, the surfactant is sodium diisooctyl succinate.
Further, the coagulating liquid is a mixture of ethanol and water, wherein the volume percent of ethanol in the coagulating liquid is at least 5%.
The polyurethane resin has the beneficial technical effects that the polyester polyol is designed to have a rigid chain and a flexible chain, a certain amount of carboxyl and hydroxyl are simultaneously controlled in the polyester polyol, the residual carboxyl in the polyester polyol is continuously grafted with polyethylene oxide, the residual hydroxyl in the polyester polyol is condensed with MDI to obtain the polyurethane resin with an aromatic polyurethane-long chain polyether structure, the molecular structure is reasonable in design, the polyurethane resin has a certain amount of rigid molecular chains and a certain amount of flexible molecular chains, so that the polyurethane resin has better strength and toughness, in addition, the grafted polyethylene oxide has a chain extension function to increase the flexibility of the molecular chains, on the other hand, the polyurethane maintains to form a regular vertical microporous structure in a solidification film-forming stage, and the problem of reduced mechanical property caused by the generation of irregular spongy cells and intramolecular crystals is solved. And then adding an anionic surfactant when preparing the polyurethane casting film liquid, so that fine adjustment of the length, the pore shape and the like of the formed vertical micropores is brought into play in the solidification film forming stage of the polyurethane, and meanwhile, the fine adjustment effect of the vertical micropores also comprises the effect of ethanol added in the solidification liquid, and when the mixed liquid of the ethanol and the water is used as the solidification liquid for solidification film forming of the polyurethane, the ethanol can control the problem of overlarge pore diameter of the vertical micropores. The polyurethane polishing pad has higher porosity, hardness and mechanical property, and meanwhile, vertical micropores in the polyurethane are uniformly distributed and regular in shape, and the surface of the polyurethane polishing pad has lower surface roughness.
Drawings
FIG. 1 is a microscopic view of the vertical micro-porous polyurethane polishing pad of example 1, wherein the polyurethane layer has a thickness of 0.7mm and a pore depth of 0.035-0.68mm, and the pore diameter is no more than 0.275mm at maximum.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods in the following examples, which are not specific to the specific conditions, are usually determined according to the national standard, and if there is no corresponding national standard, are performed according to the general international standard or the standard requirements set forth by the relevant enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
(1) The preparation of polyester polyol comprises the steps of adding bisphenol A ethoxy compound and adipic acid in a molar ratio of 1.1:1 into a reaction kettle, adding a methyl hydroquinone polymerization inhibitor accounting for 0.08% of the total mass of materials and an organotin catalyst accounting for 0.05%, carrying out normal-pressure esterification reaction for 1.5 hours at 160 ℃ under the protection of nitrogen, simultaneously draining water, vacuumizing, and heating to 220 ℃ for polycondensation until the acid value of a reaction system reaches 8.5mgKOH/g and the hydroxyl reaches 56mgKOH/g.
(2) The preparation of polyurethane resin comprises 30wt% of the polyester polyol, 7wt% of MDI, 5wt% of polyethylene oxide, 0.02wt% of a methanol end-capping agent and the balance of DMF;
Adding polyethylene oxide and half of DMF (dimethyl formamide) by weight into the obtained polyester polyol, performing grafting reaction for 4 hours at 200 ℃, then cooling to 80 ℃, adding MDI (methylene diphenyl diisocyanate) and the balance of DMF, performing reaction until the viscosity of the system reaches 150000cps, cooling to 70 ℃, adding a methanol end-capping agent for end-capping reaction for 1 hour, and continuously stirring at the temperature for 1 hour to obtain the polyurethane resin.
(3) And (3) preparing polyurethane casting solution, namely uniformly stirring and mixing 100 parts of polyurethane resin synthesized in the step (2), 3 parts of sodium diisooctyl succinate and 60 parts of DMF (dimethyl formamide), and defoaming for later use.
(4) Preparing a coagulating liquid which is a mixture of ethanol and water, wherein the volume percentage of the ethanol accounts for 5%;
And (3) coating the polyurethane film casting liquid in the step (3) on the surface of a fabric, wherein the coating thickness is at least 0.5mm, then immersing the whole body into a coagulating liquid to enable the polyurethane film casting liquid on the surface of the fabric to undergo phase inversion and solidify into a film, forming vertical micropores which are regularly arranged in a direction perpendicular to the film surface while forming the film, and then washing and drying the film to obtain the vertical microporous polyurethane polishing pad.
Example 2
(1) The preparation of polyester polyol comprises the steps of adding bisphenol A propoxy compound and adipic acid in a molar ratio of 1.2:1 into a reaction kettle, then adding methyl hydroquinone polymerization inhibitor accounting for 0.08% of the total mass of materials and organic tin catalyst accounting for 0.05%, carrying out normal-pressure esterification reaction for 1.5 hours at 160 ℃ under the protection of nitrogen, simultaneously draining water, vacuumizing, and heating to 220 ℃ for polycondensation until the acid value of a reaction system reaches 8.5mgKOH/g and the hydroxyl reaches 56mgKOH/g.
(2) The preparation of polyurethane resin comprises 25wt% of the polyester polyol, 8wt% of MDI, 6wt% of polyethylene oxide, 0.02wt% of a methanol end-capping agent and the balance of DMF;
Adding polyethylene oxide and half of DMF (dimethyl formamide) by weight into the obtained polyester polyol, performing grafting reaction for 4 hours at 200 ℃, then cooling to 80 ℃, adding MDI (methylene diphenyl diisocyanate) and the balance of DMF, performing reaction until the viscosity of the system reaches 150000cps, cooling to 70 ℃, adding a methanol end-capping agent for end-capping reaction for 1 hour, and continuously stirring at the temperature for 1 hour to obtain the polyurethane resin.
(3) And (3) preparing polyurethane casting solution, namely uniformly stirring and mixing 100 parts of polyurethane resin synthesized in the step (2), 2 parts of sodium diisooctyl succinate and 60 parts of DMF (dimethyl formamide), and defoaming for later use.
(4) Preparing a coagulating liquid which is a mixture of ethanol and water, wherein the volume percentage of the ethanol accounts for 5%;
And (3) coating the polyurethane film casting liquid in the step (3) on the surface of a fabric, wherein the coating thickness is at least 0.5mm, then immersing the whole body into a coagulating liquid to enable the polyurethane film casting liquid on the surface of the fabric to undergo phase inversion and solidify into a film, forming vertical micropores which are regularly arranged in a direction perpendicular to the film surface while forming the film, and then washing and drying the film to obtain the vertical microporous polyurethane polishing pad.
Example 3
(1) The preparation of polyester polyol comprises the steps of adding propylene glycol tetraisopropyl alcohol ether and adipic acid in a molar ratio of 1:1 into a reaction kettle, adding a methyl hydroquinone polymerization inhibitor accounting for 0.08% of the total mass of materials and an organotin catalyst accounting for 0.05%, carrying out normal-pressure esterification reaction for 2 hours at 160 ℃ under the protection of nitrogen, simultaneously draining water, vacuumizing, and heating to 220 ℃ for polycondensation until the acid value of a reaction system reaches 8.5mgKOH/g and the hydroxyl reaches 56mgKOH/g.
(2) The preparation of polyurethane resin comprises 20wt% of the polyester polyol, 9wt% of MDI, 4wt% of polyethylene oxide, 0.03wt% of a methanol end-capping agent and the balance of DMF;
Adding polyethylene oxide and half of DMF (dimethyl formamide) by weight into the obtained polyester polyol, performing grafting reaction for 4 hours at 200 ℃, then cooling to 80 ℃, adding MDI (methylene diphenyl diisocyanate) and the balance of DMF, performing reaction until the viscosity of the system reaches 150000cps, cooling to 70 ℃, adding a methanol end-capping agent for end-capping reaction for 1 hour, and continuously stirring at the temperature for 1 hour to obtain the polyurethane resin.
(3) And (3) preparing polyurethane casting solution, namely uniformly stirring and mixing 100 parts of polyurethane resin synthesized in the step (2), 5 parts of sodium diisooctyl succinate and 70 parts of DMF (dimethyl formamide), and defoaming for later use.
(4) Preparing a coagulating liquid which is a mixture of ethanol and water, wherein the volume percentage of the ethanol accounts for 5%;
And (3) coating the polyurethane film casting liquid in the step (3) on the surface of a fabric, wherein the coating thickness is at least 0.5mm, then immersing the whole body into a coagulating liquid to enable the polyurethane film casting liquid on the surface of the fabric to undergo phase inversion and solidify into a film, forming vertical micropores which are regularly arranged in a direction perpendicular to the film surface while forming the film, and then washing and drying the film to obtain the vertical microporous polyurethane polishing pad.
Comparative example 1
The preparation method of the polyurethane polishing pad of the comparative example is the same as that of example 1, except that polyethylene oxide is not added in the synthesis of the polyurethane resin in the step (2), PTMG2000 (tetrahydrofuran homo-polyether) is used as polyester diol adopted in the synthesis, and water containing 20% by volume of DMF is used as the coagulating liquid in the step (4).
The polyurethane polishing pads of the above examples and comparative examples were subjected to performance tests including shore hardness, porosity, surface roughness, rebound, tensile strength.
The method for testing the porosity can calculate the approximate porosity by observing the number of holes and the size of the holes in the surface of the polishing pad with a certain area by using a microscope.
Wherein the rebound rate (%) = (thickness after compression rebound/original thickness) ×100, in the measurement process, a pressure of 10 kg is uniformly loaded on the measured surface for 2min, and then the pressure is removed and the thickness thereof is measured, namely the thickness after compression rebound.
The results are shown in Table 1.
Table 1 comparative and example polyurethane polishing pad properties
| IC1000 | Example 1 | Comparative example 1 | Example 2 | Example 3 | |
| PU layer thickness mm | 1.2 | 0.7 | 0.7 | 0.7 | 0.7 |
| Surface porosity% | <60 | >70 | <60 | >70 | >70 |
| Tensile strength MPa | 47 | 48 | 35 | 45 | 46 |
| Rebound% | 80 | 86 | 70 | 84 | 82 |
| Surface roughness μm | 6.2 | 7.0 | 12.3 | 7.2 | 7.5 |
| Hardness Shore D | 67.8 | 75.5 | 60.4 | 73.9 | 74.6 |
The compressibility of the polishing pad determines the degree of adhesion of the polishing pad to the workpiece surface during polishing, and has a certain impact on the material removal rate and the degree of surface planarization. In the CMP process, the polishing pad is repeatedly compressed-rebound-recompressed by a varying polishing pressure or the like, which is a dynamic process. When external force is pressed to the polyurethane layer to compress the polyurethane layer, the polyurethane layer is isotropic in the axial direction under the condition that vertical micropores with ordered vertical and regular shapes are uniformly distributed in the polyurethane, namely, the polyurethane layer has elastic recovery performance after being pressed, and meanwhile, the pressure also acts on the molecular skeleton of the polyurethane. It was observed that the vertical micropores in the polyurethane layer of comparative example 1 were not uniform in size and irregular in arrangement, but the irregular vertical micropores did not bear the function of axial isotropy, and the flexible chains in the polyurethane molecular structure were a great part, which resulted in lower rebound rate after compression. The imported IC1000 polyurethane polishing pad has a foam structure similar to a sponge and has regular round cells, so that the rebound rate is good. The polyurethane polishing pad of the present invention has an equivalent effect to that of the imported product.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The preparation method of the vertical micropore polyurethane polishing pad is characterized by comprising the following steps:
coating polyurethane casting solution on the surface of a substrate, immersing the substrate in a coagulating solution to enable the polyurethane casting solution on the surface of the substrate to undergo phase inversion and solidify into a film, forming vertical micropores which are regularly arranged in the surface of the film while forming the film, and then washing and drying the film to obtain the vertical microporous polyurethane polishing pad;
the polyurethane film casting solution comprises the following materials, by weight, 100 parts of polyurethane resin, 2-5 parts of a surfactant and 30-80 parts of a solvent;
Wherein the polyurethane resin comprises, by weight, 20-30% of polyester polyol, 5-9% of MDI, 2-6% of polyethylene oxide, 0.02-0.03% of a blocking agent and the balance of a solvent;
the polyester polyol is formed by condensing bisphenol A compound and adipic acid according to a molar ratio of 1 (1-2);
the synthesis condition of the polyurethane resin is that polyester polyol, polyethylene oxide and a part of solvent are subjected to grafting reaction for 2-5 hours at 180-200 ℃, then cooled to 75-80 ℃, MDI is added to react until the viscosity of the system reaches 150000-250000cps, then cooled to 60-70 ℃, and a blocking agent is added to carry out blocking reaction for 0.5-3 hours, thus obtaining the polyurethane resin.
2. The method of making a vertical micro-porous polyurethane polishing pad of claim 1, wherein the bisphenol a compound is one or more of a malonyl tetraisopropyl alcohol ether, a bisphenol a propoxy compound, and a bisphenol a ethoxy compound.
3. The method for preparing the vertical micro-porous polyurethane polishing pad according to claim 2, wherein the synthesis process of the polyester polyol is characterized in that a polymerization inhibitor accounting for 0.08% of the total mass of materials and an organotin catalyst accounting for 0.05% of the total mass of materials are added, the reaction is carried out for 1 to 2 hours at 150 to 170 ℃ under the protection of nitrogen for drainage, and then the temperature is raised to 200 to 230 ℃ for continuous reaction until the acid value of a reaction system reaches 5 to 15mgKOH/g and the hydroxyl reaches 40 to 60mgKOH/g.
4. The method for preparing a vertical micro-porous polyurethane polishing pad according to any one of claims 1 to 3, wherein the capping agent is methanol and the solvent is DMF.
5. A method of preparing a vertical micro-porous polyurethane polishing pad according to any one of claims 1 to 3, wherein the surfactant is sodium diisooctyl succinate.
6. A method of preparing a vertical micro-porous polyurethane polishing pad according to any one of claims 1 to 3, wherein the coagulating liquid is a mixture of ethanol and water, wherein the volume percent of ethanol in the coagulating liquid is at least 5%.
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| CN202310255218.0A CN116372800B (en) | 2023-03-16 | 2023-03-16 | Preparation method of vertical microporous polyurethane polishing pad |
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| CN202310255218.0A CN116372800B (en) | 2023-03-16 | 2023-03-16 | Preparation method of vertical microporous polyurethane polishing pad |
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| CN116372800B true CN116372800B (en) | 2025-07-18 |
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| CN114701105A (en) * | 2021-04-27 | 2022-07-05 | 宁波赢伟泰科新材料有限公司 | Chemical mechanical polishing pad and preparation method thereof |
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| JP5844189B2 (en) * | 2012-03-26 | 2016-01-13 | 富士紡ホールディングス株式会社 | Polishing pad and polishing pad manufacturing method |
| TWI735101B (en) * | 2018-12-26 | 2021-08-01 | 南韓商Ｓｋｃ索密思股份有限公司 | Composition for a polishing pad, polishing pad, and process for preparing the same |
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| CN114701105A (en) * | 2021-04-27 | 2022-07-05 | 宁波赢伟泰科新材料有限公司 | Chemical mechanical polishing pad and preparation method thereof |
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