CN117801211A - Polyurethane polishing pad and preparation method thereof - Google Patents

Polyurethane polishing pad and preparation method thereof Download PDF

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Publication number
CN117801211A
CN117801211A CN202311679604.9A CN202311679604A CN117801211A CN 117801211 A CN117801211 A CN 117801211A CN 202311679604 A CN202311679604 A CN 202311679604A CN 117801211 A CN117801211 A CN 117801211A
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China
Prior art keywords
polishing pad
polyol
polyurethane polishing
parts
catalyst
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CN202311679604.9A
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Chinese (zh)
Inventor
张志强
许亮
芮自强
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Nanjing Hongbaoli New Materials Co ltd
Hongbaoli Group Co ltd
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Nanjing Hongbaoli New Materials Co ltd
Hongbaoli Group Co ltd
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Priority to CN202311679604.9A priority Critical patent/CN117801211A/en
Publication of CN117801211A publication Critical patent/CN117801211A/en
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Abstract

The invention discloses a polyurethane polishing pad and a preparation method thereof, wherein the polyurethane polishing pad is prepared from the following raw materials in parts by weight: 20-60 parts of difunctional polyol, 35-75 parts of polyfunctional polyol, 0.2-3 parts of foam stabilizer, 0.2-3 parts of catalyst and 0.2-2 parts of foaming agent; 1-30 parts of inorganic filler and 110-130 parts of isocyanate; the difunctional polyol is polyether polyol with the functionality of 2 and polyester polyol with the functionality of 2, and the mass ratio of the polyether polyol with the functionality of 2 to the polyester polyol with the functionality of 2 is (0.25-4) 1; the polyfunctional polyol is polyether polyol or polyester polyol with functionality greater than 2. The polyurethane polishing pad prepared by the invention has higher hardness and better toughness.

Description

Polyurethane polishing pad and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a polyurethane polishing pad and a preparation method thereof.
Background
The polyurethane polishing pad is a novel polishing material and is mainly used for high-precision polishing of materials such as semiconductors, displays, hard disks, glass, metals, ceramics and the like. The polyurethane polishing pad has the advantages of wear resistance, corrosion resistance, flexibility, high polishing efficiency and the like, and becomes the main stream in the current high-precision polishing field. The background of polyurethane polishing pads dates back to the 70 s of the 20 th century, when the U.S. semiconductor manufacturing industry is in a high-speed development stage, an efficient and high-precision polishing technology is needed to meet the production requirements. Through many years of research and development, polyurethane materials are gradually developed into polishing materials suitable for the semiconductor industry. Polyurethane polishing pads are continually improved and optimized as the semiconductor industry evolves, and are now becoming a mature technology and product.
Chinese patent CN 115873207B discloses a high performance CMP polyurethane polishing pad and a method for preparing the same, which adopts a conventional prepolymer method. Firstly, isocyanate, oligomer polyol and micromolecular alcohol react to generate a prepolymer A component with NCO content of 5.0-10wt.%, and then the synthesized isocyanate-terminated prepolymer A component, a chain extender B component and a hollow filler C component are uniformly mixed and then react and solidify to obtain the CMP polyurethane polishing pad. The method of the patent has complex production process and difficult control, the storage condition of the prepared prepolymer is high, the prepolymer is easy to agglomerate and deteriorate in the storage process, and the cost is high. Secondly, the viscosity of the polyurethane prepolymer is too large, so that the foaming agent cannot be uniformly dispersed, and uneven distribution of the inner cells of the product is easily caused.
Chinese patent CN 113999368B discloses a polyurethane polishing pad and a preparation method thereof, wherein an aromatic isocyanate and aliphatic isocyanate mixture is reacted with polyether polyol, microsphere foaming agent and chain extender to obtain foamed polyurethane, then the foamed polyurethane is cured by gradient heating to obtain polyurethane elastomer, and finally the polyurethane elastomer is sliced to obtain the polyurethane polishing pad. Compared with the prepolymer method, the method saves energy because of no need of preparing the prepolymer, has simple process and lower production cost, but the foaming effect of the foaming polyurethane depends on a complex gradient heating curing procedure, and is very easy to cause the unsatisfactory foaming effect, thereby influencing the performance of polyurethane polishing pad products.
Therefore, there is a need to develop a method for preparing polyurethane polishing pads that is simple in production process, low in cost, and combines hardness and toughness.
Disclosure of Invention
In order to solve the problems, the invention provides a polyurethane polishing pad and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a polyurethane polishing pad is prepared from the following raw materials in parts by weight:
the difunctional polyol is polyether polyol with the functionality of 2 and polyester polyol with the functionality of 2, and the mass ratio of the polyether polyol with the functionality of 2 to the polyester polyol with the functionality of 2 is (0.25-4) 1; the polyfunctional polyol is a polyether polyol having a functionality greater than 2.
By adopting the technical scheme, the difunctional polyol is favorable for improving the toughness of the polyurethane polishing pad, the polyester polyol can give consideration to the strength of polyurethane molecular chains, and meanwhile, the difunctional polyol is cooperated with the difunctional polyol, so that the crosslinking of polyurethane polishing pad molecules can be ensured, and the polyurethane polishing pad has better hardness. And the hardness and toughness of the polyurethane polishing pad material can be better controlled by adjusting the proportion of different polyols.
Further, the inorganic filler is selected from at least one of boron carbide, cerium oxide, zirconium oxide, calcium carbonate and silicon dioxide having an average particle diameter of 70 to 120 nm. Further, the average particle diameter of the inorganic filler is preferably 80 to 100nm.
The inorganic filler mainly improves the hardness and mechanical strength of the foam, and the hardness of the polyurethane polishing pad can be enhanced and the production cost can be reduced by selecting the inorganic filler.
Further, the foam stabilizer is an organosilicon surfactant containing Si-O-C or Si-C bond in its molecular structure, preferably at least one of model SD624 produced by M8805, B8525, B8544, suzhou Side New Material technology Co., ltd and model EPR-S-55 produced by Shanghai specialty Chemie Co., ltd.
The foam stabilizer is cooperated with the polyol, so that the foam stability is high.
Further, the catalyst is an amine catalyst, an organometallic salt catalyst or a delayed catalyst, preferably selected from the group consisting of bis (dimethylaminoethyl ether), dimethylcyclohexane, tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, potassium isooctanoate, dibutyltin dilaurate,and at least one of the model xfas 3015 manufactured by the company "Shanghai"), inc.
The catalyst is used for regulating the foaming reaction rate and the gel reaction rate in the foaming process, and the two reaction rates can be balanced by adopting the catalyst, so that the polyurethane polishing pad product with excellent performance is obtained.
Further, the foaming agent is at least one selected from water, cyclopentane (CP) and HCFC-141 b.
The foaming agent is cooperated with the polyol, so that the foaming effect is better.
Further, the isocyanate is polymethylene polyphenyl polyisocyanate, preferably any one of PM-200 and PM-400 manufactured by Wanhua chemical group Co., ltd., M20s and M50s manufactured by Basoff Co., ltd.
The isocyanate and the polyol cooperate to obtain the polyurethane polishing pad product with excellent performance.
The preparation method of any one of the polyurethane polishing pads comprises the following steps:
(1) Uniformly mixing the difunctional polyol, the polyfunctional polyol, the foam stabilizer, the catalyst, the foaming agent and the inorganic filler according to a proportion to form a material A;
(2) Adding isocyanate into the material A according to a proportion, immediately stirring and uniformly mixing at a high speed, and pouring into a mould for foaming;
(3) And (3) curing the polyurethane foam after foaming at normal temperature, demolding and slicing to obtain the polyurethane polishing pad.
Further, the polyurethane polishing pad prepared in the step (3) has a Shore A hardness of 82-97.
The invention has the beneficial effects that:
1. the polyurethane polishing pad prepared by the invention has higher hardness and better toughness.
2. The polyurethane polishing method for foaming and preparing polyurethane by adopting the one-step method does not need secondary processing, simplifies the production process, shortens the production period, improves the production efficiency and reduces the production cost.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
The invention uses the following raw materials:
difunctional polyol:
difunctional polyether polyol A, hongbaoli group Co., ltd., has a functionality of 2 and a hydroxyl value of 224mgKOH/g;
difunctional polyester polyol B, red Baoli group Co., ltd., has a functionality of 2 and a hydroxyl value of 293mgKOH/g;
polyfunctional polyol:
a polyfunctional polyol C, red Baoli group Co., ltd., having a functionality of 3 and a hydroxyl value of 168mgKOH/g;
polyfunctional polyol D, red Baoli group Co., ltd., functionality of 3, hydroxyl value of 340mgKOH/g;
a polyfunctional polyol E, red Baoli group Co., ltd., having a functionality of 3.6 and a hydroxyl value of 450mgKOH/g;
a polyfunctional polyol F, red Baoli group Co., ltd., having a functionality of 4.1 and a hydroxyl value of 425mgKOH/g;
a polyfunctional polyol G, red Baoli group Co., ltd., having a functionality of 4.2 and a hydroxyl value of 447mgKOH/G;
the polyfunctional polyol H, red Baoli group Co., ltd., has a functionality of 6 and a hydroxyl value of 410mgKOH/g;
a polyfunctional polyol I, red Baoli group Co., ltd., having a functionality of 6 and a hydroxyl value of 470mgKOH/g;
isocyanates PM-200 and PM-400, wanhua chemical group Co., ltd;
isocyanates M20s and M50s, basf, inc.
Example 1
5 parts of difunctional polyether polyol A, 15 parts of difunctional polyester polyol B, 25 parts of polyfunctional polyol C, 50 parts of polyfunctional polyol I, 8525 parts of foam stabilizer B, 0.1 part of catalyst bis-dimethylaminoethyl ether, 0.3 part of catalyst dimethyl cyclohexane, 0.3 part of catalyst 2-hydroxy-N, N, N-trimethyl-1-propylamine formate and catalyst1.0 part of inorganic filler boron carbide 30 parts and foaming agent water 0.2 parts are uniformly mixed, 110 parts of isocyanate PM-400 is added into the mixed material, immediately stirred at a high speed for 6 seconds, and immediately poured into a mold for foaming and curing for 3 hours. Slicing after curing to obtain the No. 1 polyurethane polishing pad.
Example 2
15 parts of difunctional polyether polyol A, 15 parts of difunctional polyester polyol B, 20 parts of polyfunctional polyol E, 25 parts of polyfunctional polyol I, 20 parts of polyfunctional polyol H, 1.5 parts of foam stabilizer M8805 and catalysis0.1 part of dibutyltin dilaurate, 0.8 part of dimethylcyclohexane as a catalyst, 0.2 part of tris (dimethylaminopropyl) hexahydrotriazine as a catalyst and a catalyst1.9 parts of inorganic filler cerium oxide 5 parts, 0.2 part of foaming agent water and 0.5 part of foaming agent CP are uniformly mixed, 120 parts of isocyanate PM-200 is added into the mixed material, immediately stirred at a high speed for 6 seconds, immediately poured into a mold, foamed and cured for 3 hours. Slicing after curing to obtain the No. 2 polyurethane polishing pad.
Example 3
15 parts of difunctional polyether polyol A, 30 parts of difunctional polyester polyol B, 20 parts of polyfunctional polyol F, 30 parts of polyfunctional polyol G, 1.0 part of foam stabilizer B8544, 0.3 part of catalyst dimethylcyclohexane, 0.5 part of catalyst potassium isooctanoate, 20 parts of inorganic filler zirconia, 0.2 part of foaming agent water and 1 part of foaming agent HCFC-141b are uniformly mixed, 120 parts of isocyanate M20S is added into the mixed materials, immediately stirred at a high speed for 6 seconds, and immediately poured into a mold for foaming and curing for 3 hours. Slicing after curing to obtain the No. 3 polyurethane polishing pad.
Example 4
15 parts of difunctional polyether polyol A, 45 parts of difunctional polyester polyol B, 15 parts of polyfunctional polyol D, 15 parts of polyfunctional polyol G, 20 parts of polyfunctional polyol H, 624.8 parts of SD624 of Suzhou New Material science and technology Co., ltd, 0.3 part of catalyst dimethylcyclohexane, 0.3 part of catalyst 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 15 parts of inorganic filler silica and 0.5 part of foaming agent water are uniformly mixed, 110 parts of isocyanate M50S is added into the mixed materials, immediately stirred at a high speed for 6 seconds, and then immediately poured into a mold for foaming and curing for 3 hours. Slicing after curing to obtain the No. 4 polyurethane polishing pad.
Example 5
10 parts of difunctional polyether polyol A, 40 parts of difunctional polyester polyol B, 10 parts of polyfunctional polyol C, 35 parts of polyfunctional polyol E, 0.3 part of foam stabilizer B8525, 0.3 part of catalyst dimethylcyclohexane, 0.1 part of XFAD3015 of catalyst Yingzhuang specialty Chemie (Shanghai) Co., ltd, 5 parts of inorganic filler calcium carbonate and 2 parts of foaming agent HCFC-141b are uniformly mixed, 130 parts of isocyanate M20S is added into the mixed materials, immediately stirred at a high speed for 6 seconds, and immediately poured into a mold for foaming and curing for 3 hours. Slicing after curing to obtain the No. 5 polyurethane polishing pad.
Example 6
10 parts of difunctional polyether polyol A, 40 parts of difunctional polyester polyol B, 20 parts of polyfunctional polyol E, 20 parts of polyfunctional polyol I, 0.3 part of foam stabilizer B8544, 0.3 part of catalyst dimethylcyclohexane, 0.2 part of XFAD3015 of catalyst winning specialty Chemie (Shanghai) Co., ltd, and catalyst1.0 part of inorganic filler boron carbide 3 parts and foaming agent water 0.2 parts are uniformly mixed, 110 parts of isocyanate PM-400 is added into the mixed material, immediately stirred at a high speed for 6 seconds, and immediately poured into a mold for foaming and curing for 3 hours. Slicing after curing to obtain the No. 6 polyurethane polishing pad.
Example 7
10 parts of difunctional polyether polyol A, 40 parts of difunctional polyester polyol B, 15 parts of polyfunctional polyol D, 30 parts of polyfunctional polyol F, 0.5 part of foam stabilizer B8525, 1.0 part of EPR-S-55 of foam stabilizer winning specialty chemical (Shanghai) Co., ltd, 0.3 part of catalyst dimethylcyclohexane, 0.2 part of catalyst winning specialty chemical (Shanghai) Co., XFAD3015 and 0.2 part of catalyst1.0 part of inorganic filler boron carbide 1 part and 0.2 part of foaming agent water are uniformly mixed, 130 parts of isocyanate PM-400 is added into the mixed material, immediately stirred at a high speed for 6 seconds, and immediately poured into a mold for foaming and curing for 3 hours. Slicing after curing to obtain the 7# polyurethane polishing pad.
The prepared 1-7# polyurethane polishing pad was subjected to the following performance characterization:
(1) Density: the test was carried out according to GB/T6343-2009 foam and determination of rubber apparent density.
(2) Hardness: the test was performed according to GB/T2411-2008/ISO 868:2003 for plastics and hard rubber using a durometer to determine indentation hardness (Shore hardness). Hardness measurement of polyurethane polishing pad Material synthesized according to the present invention Using Japan three-amount rubber Silicone Shore durometer type LX-A (softer rubber measurement)
(3) Toughness: the test was carried out according to the basic bending test part 1 of the test for bending properties of rigid foams, GB/T8812.1-2007/ISO 1209-1:2004. The toughness of the materials was characterized by testing the deformation of the polyurethane polishing pad materials synthesized according to the present invention upon fracture in a bending test using a universal tensile tester.
The test results are summarized in table 1:
TABLE 1 polyurethane polishing pad Performance
Polishing pad numbering Density (kg/m 3) Hardness (Shore A) Bending deformation (mm) Toughness of
1# 370.5 92 1.89 Poor quality
2# 341.9 87 2.24 Preferably, it is
3# 357.6 93 2.33 Preferably, it is
4# 346.1 85 3.60 Good (good)
5# 322.8 82 3.33 Good (good)
6# 381.7 97 3.57 Good (good)
7# 406.7 95 3.14 Good (good)
As is clear from Table 1, the addition of the difunctional polyol can improve the toughness of the polyurethane polishing pad, and by adjusting the addition amount of the difunctional polyol and the ratio of the difunctional polyether polyol to the polyester polyol, the polyurethane polishing pad excellent in hardness and toughness can be obtained by foaming in one step. The results of analysis of Table 1 show that the 6# polyurethane polishing pad has good toughness and the Shore A hardness is highest.
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 (9)

1. The polyurethane polishing pad is characterized by being prepared from the following raw materials in parts by weight:
the difunctional polyol is polyether polyol with the functionality of 2 and polyester polyol with the functionality of 2, and the mass ratio of the polyol with the functionality of 2 to the polyester polyol with the functionality of 2 is (0.25-4): 1; the polyfunctional polyol is polyether polyol or polyester polyol with functionality greater than 2.
2. The polyurethane polishing pad according to claim 1, wherein the inorganic filler is at least one selected from the group consisting of boron carbide, cerium oxide, zirconium oxide, calcium carbonate and silicon dioxide having an average particle diameter of 70 to 120 nm.
3. The polyurethane polishing pad of claim 1, wherein the foam stabilizer is a silicone surfactant having Si-O-C or Si-C bonds in the molecular structure.
4. A polyurethane polishing pad according to claim 3, wherein said foam stabilizer is selected from at least one of the group consisting of M8805, B8525, B8544, SD624 model by scotch new materials technology, inc.
5. The polyurethane polishing pad of claim 1, wherein the catalyst is an amine catalyst, an organometallic salt catalyst, or a delay catalyst.
6. The polyurethane polishing pad of claim 5 wherein the catalyst is selected from the group consisting of bis-dimethylaminoethyl ether, dimethyl cyclohexane, tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N-trimethyl-1-propylamine formate, potassium isooctanoate, dibutyltin dilaurate, and,JXP509 and XFAD3015, available from Shanghai specialty Chemie, inc.
7. The polyurethane polishing pad of claim 1, wherein the isocyanate is polymethylene polyphenyl polyisocyanate.
8. The method for producing a polyurethane polishing pad according to any one of claims 1 to 7, comprising the steps of:
(1) Uniformly mixing the difunctional polyol, the polyfunctional polyol, the foam stabilizer, the catalyst, the foaming agent and the inorganic filler according to a proportion to form a material A;
(2) Adding isocyanate into the material A according to a proportion, immediately stirring and uniformly mixing at a high speed, and pouring into a mould for foaming;
(3) And (3) curing the polyurethane foam after foaming at normal temperature, demolding and slicing to obtain the polyurethane polishing pad.
9. The method of claim 8, wherein the polyurethane polishing pad produced in step (3) has a shore a hardness of 82-97.
CN202311679604.9A 2023-12-08 2023-12-08 Polyurethane polishing pad and preparation method thereof Pending CN117801211A (en)

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Application Number Priority Date Filing Date Title
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Publications (1)

Publication Number Publication Date
CN117801211A true CN117801211A (en) 2024-04-02

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Application Number Title Priority Date Filing Date
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