Modified polyamide resin based on ion imprinting technology and preparation method and application thereof
By grafting carboxyl and amide bonds onto PA66 resin and combining this with ion imprinting technology, a modified polyamide resin was prepared. This solved the problem of poor metal ion removal in photoresist, achieving ppb-level metal ion removal and improving chip performance and yield.
Patent Information
- Application Number
- CN202511732923.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-24
- Publication Date
- 2026-02-10
AI Technical Summary
Existing photoresists are not effective at removing metal ions, especially in organic solutions where it is difficult to achieve the ppb level, which affects chip performance and yield.
Ion imprinting technology was used to modify polyamide resin. By grafting carboxyl groups and amide bonds onto PA66 resin and then imprinting it with a metal ion template solution, the adsorption capacity and specific recognition of metal ions were enhanced.
This achievement reduces the metal ion concentration in photoresist to the ppb level, meeting the requirements of the international semiconductor technology roadmap and improving chip quality and reliability.
Smart Images
Figure CN121495050A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photoresist purification technology. More specifically, it relates to a modified polyamide resin based on ion imprinting technology, its preparation method, and its applications. Background Technology
[0002] Photoresist is an indispensable key material in chip manufacturing. In the photolithography process, photoresist is uniformly coated on the wafer surface. Subsequently, through photolithography and etching processes, complex patterns are precisely transferred onto the wafer, thereby constructing the chip's intricate circuit structure. The entire chip manufacturing process involves the construction of multiple alternating conductive and insulating layers, which typically requires repeating dozens of photolithography steps using different types of photoresist.
[0003] During chip manufacturing, metal ions in photoresist can penetrate into the silicon substrate and oxide layer. Under the influence of an electric field, these metal ions migrate within the chip, altering the charge distribution and interfering with the internal electric field. This, in turn, affects the charge transport characteristics, leading to performance degradation and reduced yield. Therefore, strict control of the metal ion concentration in photoresist is essential to ensure high chip quality and reliability. The international semiconductor technology roadmap sets ppb-level requirements for metal ion content in photoresist. Achieving metal ion removal from photoresist is a key challenge in photoresist purity control. Therefore, developing a material capable of reducing the metal ion content in photoresist to the ppb level is of significant scientific importance and promising application prospects.
[0004] Polyamide 66 (PA66) contains lone pairs of electrons in its carbonyl oxygen atom and amino nitrogen atom in its amide bond. Metal ions can act as electron donors, while metal ions can provide empty electron acceptor orbitals. Complexation and coordination can occur between the two, thus achieving the adsorption of metal ions. PA66 has been widely studied and applied in the field of filter membranes. However, the main materials in photoresists are mostly macromolecular polymers, which easily form scaffolds on the membrane, leading to clogging and affecting the filtration effect.
[0005] Currently, ion exchange resins are commonly used adsorbents for removing metal ions. Their removal efficiency primarily stems from the functionalized groups grafted onto them. While they exhibit excellent removal performance in aqueous solutions, their effectiveness in organic solutions is poor. This is mainly because metal ions exist in different forms in aqueous and organic solutions. In organic solutions, some metal ions exist as ion pairs, and in nonpolar solvents, the binding of cation and anion pairs is more robust, leading to a weakening of the ion's charge. Simultaneously, metal ions undergo complexation reactions with functional groups such as hydroxyl groups and ether bonds in organic solvents, further reducing the number of free metal ions. The weakened charge of metal ions and the lower concentration of free metal ions reduce the efficiency of ion exchange, resulting in poor metal ion removal performance of ion exchange resins in organic solvents. Therefore, it is essential to research a modified PA66 resin adsorbent with a large specific surface area and high adsorption capacity. Summary of the Invention
[0006] In view of the above-mentioned shortcomings, the first objective of this invention is to provide a method for preparing modified polyamide resin based on ion imprinting technology. This method is simple to operate and the conditions are controllable. The preparation process does not require high-temperature or high-pressure equipment, and the solvent used has a low boiling point, is not prone to residue, and is easily removed during post-processing.
[0007] A second objective of this invention is to provide a modified polyamide resin based on ion imprinting technology.
[0008] The third objective of this invention is to provide a method for removing metal ions from photoresist.
[0009] To achieve the first objective mentioned above, the present invention adopts the following technical solution: This invention discloses a method for preparing modified polyamide resin based on ion imprinting technology, comprising the following steps: (1) Disperse PA66 resin in water, add initiator and dispersant, shake vigorously (the purpose is to make the initiator evenly adhere to the surface of PA66 resin), continue to add functional monomer to obtain reaction solution, and stir the reaction under closed conditions; wherein, the functional monomer is a monomer containing carboxyl group and unsaturated double bond. (2) After the reaction is complete, water is added to the reaction solution to separate the solid and liquid. The separated solid is activated with an activator, washed, and dried to obtain carboxyl-modified PA66 resin. (3) Add dispersant and metal ion template solution to carboxyl-modified PA66 resin, stir evenly, add excess deionized water to quench the reaction, stir vigorously and let stand, precipitate, separate solid and liquid, soak the separated solid with eluent, wash, then soak the solid with activator, wash, dry, and obtain carboxyl-modified metal ion imprinted PA66 resin.
[0010] Furthermore, the functional monomer is selected from one or more of acrylic acid, methacrylic acid, 4-pentenoic acid, itaconic acid, butenoic acid, and maleic acid.
[0011] Furthermore, the concentration of the functional monomer in the reaction solution is 2-4 mol / L.
[0012] Furthermore, the initiator is selected from one or more of benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxide, ammonium persulfate, isopropyl hydroperoxide, diisopropylbenzene hydroperoxide, and tert-butanol peroxide.
[0013] Furthermore, the amount of initiator added is 10-20% of the mass of PA66 resin.
[0014] Furthermore, the dispersant is selected from one or more of Tween 80, Tween 20, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate, and its mass fraction is 1-2% of the solution in the system.
[0015] Furthermore, in step (1), the reaction temperature is 383-403K and the reaction time is 6-10h.
[0016] Furthermore, the solid-liquid separation operation in step (2) includes decantation and centrifugation.
[0017] Furthermore, the solvent used for washing in step (2) is an organic solvent that is miscible with water in any proportion and has a low boiling point, selected from one or more of methanol, acetone, ethanol, isopropanol, n-propanol, and ethylene glycol.
[0018] Furthermore, the activator is selected from tetramethylammonium hydroxide at a concentration of 5-10%.
[0019] Furthermore, the eluent is selected from a dilute acid solution with a concentration of 5-10%, such as dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, and other inorganic acids.
[0020] Furthermore, the metal ion template solution is a mixed solution prepared from metal salt, water, and ethanol.
[0021] Furthermore, the molality of the metal salt in the metal ion template solution is 3.0-5.0 mol / kg; for example, the molality of the metal salt in the metal ion template solution can be 3.0 mol / kg, 3.5 mol / kg, 4.0 mol / kg, 4.5 mol / kg, 5.0 mol / kg, etc.
[0022] Furthermore, the metal ions contained in the metal ion template solution are selected from Ca... 2+ Fe 3+ Mg 2+ Mn 2+ Cu2+ Li + Na + K + Cr 3+ Ni 2+ One or more of them.
[0023] Furthermore, the volume ratio of water to ethanol in the metal ion template solution is 1.8:1-4:1; for example, the volume ratio of water to ethanol in the metal ion template solution can be 1.8:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, etc.
[0024] Furthermore, the mass-to-volume ratio of carboxyl-modified PA66 resin to metal ion template solution is 1 g / 5-20 ml.
[0025] To achieve the second objective mentioned above, the present invention adopts the following technical solution: This invention discloses a modified polyamide resin based on ion imprinting technology prepared by the preparation method described above.
[0026] Both the amide bonds on PA66 and the grafted carboxyl groups possess coordination capabilities, enabling them to bind with metal ions. The grafting of carboxyl groups, along with the imprinted pores, increases the specific surface area of the material, thereby increasing its adsorption capacity. Ion imprinting on PA66 resin, using metal ions as templates, allows for the specific recognition and binding of metal ions. Through the combined action of the amide bonds on PA66, the grafted carboxyl groups, and the imprinted pores using metal ions as templates, once adsorbed, metal ions are not easily detached, allowing the metal ion concentration in the photoresist solution to reach a low level, at the ppb level.
[0027] To achieve the third objective mentioned above, the present invention adopts the following technical solution: This invention discloses a method for removing metal ions from photoresist, comprising the following steps: The modified polyamide resin described above is mixed with a solution containing photoresist resin, and the mixture is shaken at a constant temperature. After shaking, the mixture is filtered to remove metal ions from the photoresist resin. The photoresist resin treated by the above method has a single metal ion content reduced to below 5 ppb, which meets the current requirements for photoresist purity control, that is, the metal ion content in the photoresist reaches the ppb level.
[0028] It should be noted that the aforementioned photoresist resin refers to the photoresist product undergoing purification treatment, which may contain Li. + Na + Mg 2+ A1 3+ K + Ca2+ Cr 3+ Mn 2+ Fe 3+ Ni 2+ Cu 2+ and Sn 2+ One or more metal ions are involved. The modified polyamide resin refers to the carboxyl-modified metal ion imprinted PA66 resin prepared according to the aforementioned preparation method, and has undergone a pretreatment step before mixing with the photoresist resin to ensure that the concentration of metal ions dissolved in pure water and organic solvents is less than 1 ppb. This is mainly to eliminate the interference caused by metal ion imprinting technology.
[0029] According to an embodiment of the present invention, the system in which the photoresist resin to be treated exists is an organic solvent system in which the photoresist resin is dispersed, that is, the photoresist to be treated exists in a form mixed with an organic solvent. For example, the organic solvent is at least one of ester organic solvents, alcohol organic solvents, and ether organic solvents commonly used in the field of photoresists; for example, the ester organic solvent is propylene glycol methyl ether acetate (PGMEA).
[0030] Furthermore, each 2.5g of the modified polyamide resin corresponds to purifying 10-200mL of a solution containing photoresist resin with a metal ion concentration of less than 300ppb.
[0031] Furthermore, each 2.5g of the modified polyamide resin corresponds to purifying 10-200mL of a solution containing photoresist resin with a metal ion concentration greater than 50ppb and less than 300ppb.
[0032] Furthermore, the isothermal oscillation temperature is room temperature, the isothermal oscillation time is 180-500 min, and the oscillation speed is 100-200 rpm.
[0033] Technicians can select a more suitable carboxyl-modified metal ion imprinted PA66 resin to treat the photoresist based on the different target metal ions to be removed, in order to improve its adsorption performance.
[0034] The beneficial effects of this invention are as follows: This invention provides a modified polyamide resin prepared using carboxylic acid modification and ion imprinting technology. On the one hand, by grafting specific carboxylic acid structures onto PA66 resin, the coordination ability of the carboxylic acid structure can enhance the binding ability to some metal ions, increasing its adsorption capacity. On the other hand, using ion imprinting technology, one or more metal ions are used as templates, which increases the specific surface area of the material, giving PA66 resin more binding sites for metal ions, and leaving a three-dimensional porous structure that can specifically bind to one or more ions, enhancing the recognition and binding ability of specific metal ions. The ion imprinting technology in this invention differs from conventional ion imprinting technology. The mixed solution of metal ions, water, and ethanol simultaneously introduces template metal ions and softens the host material. PA66 remains stable in water or ethanol, while the metal ions in the mixed solution create imprints in PA66 resin by binding with the amide bonds and breaking hydrogen bonds. Subsequently, water is added to complete the resin curing. The entire imprinting process can be completed within 10 minutes, which is convenient and fast.
[0035] Modified polyamide resins prepared by carboxylic acid modification and ion imprinting exhibit excellent removal capabilities in removing metal ions from photoresists, reducing the metal ion content in photoresists to the ppb level, and are also suitable for applications that require the simultaneous removal of multiple metal ions. Attached Figure Description
[0036] Figure 1 The image shows the FT-IR spectrum of the acrylic acid-modified PA66 resin prepared in Example 1. Detailed Implementation
[0037] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0038] Example 1: Grafting acrylic acid onto the surface of PA66 resin This example provides a method for preparing PA66 resin by grafting acrylic acid onto its surface, specifically including the following steps: 1) Take 10.0 g of PA66 resin granules (200 mesh) and add them to a 250 mL separatory funnel. Add methanol, wash and extract, and then dry.
[0039] 2) Add dry PA66 resin, magnetic ball, 250 mL deionized water, 1.0 g benzoyl peroxide, and 3.0 mL Tween 80 to a 500 mL round-bottom flask. Shake vigorously for 5 min, then add 68 mL acrylic acid, stir, and react at 90 °C in a sealed container for 8 h.
[0040] 3) After the reaction is stopped, add deionized water and stir to separate the carboxyl PA66 and homopolymerized polyacrylic acid. Centrifuge to separate the solid, wash with deionized water several times, transfer the solid into a 500 mL round bottom flask, add 300 mL of deionized water and a magnetic stir bar, stir and heat at 105 °C, and reflux.
[0041] 4) Centrifuge to separate the solid, soak the separated solid in 5% dilute hydrochloric acid for 5 hours, wash with deionized water multiple times, then soak the solid in 5% TMAH, wash with deionized water until neutral, centrifuge, and dry to obtain acrylic acid modified PA66 resin.
[0042] Depend on Figure 1 The FT-IR results show that 1720.5 cm⁻¹ -1 The carboxyl peak at the point confirms that acrylic acid was successfully grafted onto the surface of PA66 resin.
[0043] Example 2: Preparation of carboxyl-modified calcium ion-imprinted PA66 resin Mix 65 mL of deionized water and 35 mL of ethanol in a 250 mL beaker. Weigh 61.6 g of anhydrous CaCl2 and slowly add it to the beaker. Stir with a magnetic stirrer until the solid is completely dissolved to obtain a calcium ion template solution.
[0044] Take 25 mL of deionized water into a 250 mL beaker, add 10 g of the acrylic-modified PA66 resin granules (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared calcium ion imprinting solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decant to obtain a solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, wash the solid again with plenty of deionized water, soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic-modified calcium ion imprinted PA66 resin. Its specific surface area was measured to be 0.538 m². 2 / g.
[0045] Example 3: Preparation of carboxyl-modified magnesium ion-imprinted PA66 resin Measure 120 mL of deionized water and 32 mL of ethanol into a 250 mL beaker and mix them. Weigh 66.7 g of anhydrous MgSO4 and slowly add it into the beaker. Add a magnetic stir bar and heat to 60 °C until the solid is completely dissolved to obtain a magnesium ion template solution.
[0046] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of the acrylic-modified PA66 resin (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared magnesium ion imprinting solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decant to obtain a solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, wash the solid again with plenty of deionized water, soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic-modified magnesium ion imprinted PA66 resin. Its specific surface area was measured to be 0.519 m². 2 / g.
[0047] Example 4: Preparation of carboxyl-modified iron ion-imprinted PA66 resin Measure 90 mL of deionized water and 32 mL of ethanol into a 250 mL beaker and mix them. Weigh 60.0 g of anhydrous FeCl3 and slowly add it into the beaker. Stir with a magnetic stirrer until the solid is completely dissolved to obtain an iron ion template solution.
[0048] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of acrylic acid-modified PA66 resin granules (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared iron ion template solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decantation to obtain a reddish-brown solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, the solid changes from reddish-brown to white, wash the solid again with plenty of deionized water, then soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic acid-modified iron ion imprinted PA66 resin. Its specific surface area was measured to be 0.612 m². 2 / g.
[0049] Example 5: Preparation of carboxyl-modified iron and calcium mixed ion-imprinted PA66 resin Measure 90 mL of deionized water and 32 mL of ethanol and mix them in a 250 mL beaker. Weigh 30.8 g of anhydrous CaCl2 and 30.0 g of anhydrous FeCl3 and slowly add them to the beaker. Stir with a magnetic stirrer until the solid is completely dissolved to obtain a calcium and iron ion template solution.
[0050] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of acrylic acid-modified PA66 resin granules (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared calcium and iron ion template solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decantation to obtain a reddish-brown solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, the solid changes from reddish-brown to white, wash the solid again with plenty of deionized water, then soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic acid-modified iron and calcium mixed ion imprinted PA66 resin. Its specific surface area was measured to be 0.589 m². 2 / g.
[0051] Example 6: Preparation of carboxyl-modified magnesium and calcium mixed ion-imprinted PA66 resin Measure 90 mL of deionized water and 32 mL of ethanol and mix them in a 250 mL beaker. Weigh 33.3 g of anhydrous MgSO4 and 30.8 g of anhydrous CaCl2 and slowly add them to the beaker. Add a magnetic stir bar and heat to 60 °C until the solid is completely dissolved to obtain a calcium and magnesium ion template solution.
[0052] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of acrylic acid-modified PA66 resin granules (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared calcium and magnesium ion imprinting solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decant to obtain a solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, wash the solid again with plenty of deionized water, soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic acid-modified magnesium and calcium mixed ion imprinted PA66 resin. Its specific surface area was measured to be 0.531 m². 2 / g.
[0053] Example 7: Preparation of carboxyl-modified manganese, copper, and calcium mixed ion-imprinted PA66 resin Measure 90 mL of deionized water and 32 mL of ethanol and mix them in a 250 mL beaker. Weigh 17.4 g of anhydrous MnCl2, 23.6 g of CuCl2·2H2O and 20.5 g of anhydrous CaCl2 and slowly add them to the beaker. Stir with a magnetic stirrer until the solid is completely dissolved to obtain a calcium, copper and manganese ion template solution.
[0054] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of the acrylic-modified PA66 resin (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared calcium, copper, and manganese ion template solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decant to obtain a blue-green solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, the solid changes from blue-green to white, wash the solid again with plenty of deionized water, then soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic-modified manganese, copper, and calcium mixed ion-imprinted PA66 resin. Its specific surface area was measured to be 0.507 m². 2 / g.
[0055] Example 8: Preparation of carboxyl-modified iron, magnesium, and calcium mixed ion-imprinted PA66 resin Measure 90 mL of deionized water and 32 mL of ethanol and mix them in a 250 mL beaker. Weigh 20.0 g of anhydrous FeCl3, 22.2 g of MgSO4 and 30.8 g of anhydrous CaCl2 and slowly add them to the beaker. Stir with a magnetic stirrer until the solids are completely dissolved to obtain an iron-magnesium-calcium ion template solution.
[0056] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of the acrylic-modified PA66 resin (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and add magnetic stirring to evenly disperse the PA66 resin in the water. Slowly add the prepared iron, magnesium, and calcium ion imprinting solution to the water. Stir vigorously for 10 min, then continue to add excess deionized water to quench the reaction. Centrifuge and decantation to obtain a reddish-brown solid, wash thoroughly with plenty of water, soak the separated solid in 5% dilute hydrochloric acid, the solid changes from reddish-brown to white, wash the solid again with plenty of deionized water, then soak the separated solid in 5% TMAH solution, wash the solid again with plenty of deionized water, and dry the solid to obtain a white powder, which is the acrylic-modified iron, magnesium, and calcium mixed ion imprinted PA66 resin. Its specific surface area was measured to be 0.555 m². 2 / g.
[0057] Comparative Example 1: Preparation of Carboxyl-Modified Iron Ion Imprinted PA66 Resin Measure 90 mL of deionized water and 32 mL of ethanol and mix them in a 250 mL beaker. Weigh 100.0 g of anhydrous FeCl3 and slowly add it to the beaker. Stir with a magnetic stirrer until the solid is completely dissolved to obtain an iron ion template solution.
[0058] Take 30 mL of deionized water into a 250 mL beaker, add 10 g of the acrylic-modified PA66 resin granules (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and stir with a magnetic stirrer to evenly disperse the PA66 in the water. Slowly add the prepared iron ion template solution to the water. After stirring vigorously for 2 minutes, it was found that the PA66 resin aggregated, possibly because the concentration of the iron ion template solution was too high, causing the PA66 resin to partially dissolve and transform into a molten state.
[0059] Comparative Example 2: Preparation of Carboxyl-Modified Calcium Ion Imprinted PA66 Resin Mix 65 mL of deionized water and 35 mL of ethanol in a 250 mL beaker. Weigh 61.6 g of anhydrous CaCl2 and slowly add it to the beaker. Stir with a magnetic stirrer until the solid is completely dissolved to obtain a calcium ion template solution.
[0060] Take 25 mL of deionized water into a 250 mL beaker, add 10 g of the acrylic-modified PA66 resin granules (200 mesh) prepared in Example 1 and 1.5 mL of Tween 80, and stir with a magnetic stirrer to evenly disperse the PA66 resin in the water. Slowly add the prepared calcium ion imprinting solution to the water. Stir vigorously for 10 min, and then continue to add excess deionized water to quench the reaction. Centrifuge and decant to obtain a solid, wash thoroughly with plenty of water, and dry the solid to obtain a white powder, which is the acrylic-modified calcium ion imprinted PA66 resin.
[0061] Example 9: Removal of metal ions from photoresist using carboxyl-modified calcium ion-imprinted PA66 resin 2.5 g of the acrylic-modified calcium ion-imprinted PA66 resin prepared in Example 2 was placed in a 50 mL sample bottle, and 50 mL of the photoresist solution to be purified was added. The bottle was then placed in a constant temperature shaker (25℃, 100 rpm) and shaken for 300 min. A sample was then taken, filtered through a filter membrane, and the metal ion concentration was measured using ICP-MS. The ICP-MS test results are shown in Table 1. The acrylic-modified calcium ion-imprinted PA66 resin exhibits excellent adsorption performance for calcium ions, significantly better than the unmodified PA66 resin granules, and can reduce the metal ion content in the photoresist to the ppb level.
[0062] Table 1
[0063] Comparative Example 3: Removal of Metal Ions from Photoresist by Carboxyl-Modified Calcium Ion Imprinted PA66 Resin 2.5 g of the acrylic-modified calcium ion-imprinted PA66 resin prepared in Comparative Example 2 was placed in a 50 mL sample vial, and 50 mL of the photoresist solution to be purified was added. The vial was then placed in a constant temperature shaker (25℃, 100 rpm) and shaken for 300 min. A sample was then taken, filtered through a filter membrane, and the metal ion concentration was measured using ICP-MS. The ICP-MS test results are shown in Table 2. The acrylic-modified calcium ion-imprinted PA66 resin almost lost its adsorption effect on calcium ions, presumably because the calcium ions were not washed out of the PA66 resin and still occupied the active sites.
[0064] Table 2
[0065] Example 10: Removal of metal ions from photoresist using carboxyl-modified magnesium ion-imprinted PA66 resin 2.5 g of the acrylic-modified magnesium ion-imprinted PA66 resin prepared in Example 3 was placed in a 50 mL sample bottle, and 50 mL of the photoresist solution to be purified was added. The bottle was then placed in a constant temperature shaker (25℃, 100 rpm) and shaken for 300 min. A sample was then taken, filtered through a filter membrane, and the metal ion concentration was measured using ICP-MS. The ICP-MS test results are shown in Table 3. The acrylic-modified magnesium ion-imprinted PA66 resin exhibits excellent adsorption performance for magnesium ions, significantly better than the unmodified PA66 resin granules, and can reduce the metal ion content in the photoresist to the ppb level.
[0066] Table 3
[0067] Example 11: Removal of metal ions from photoresist using carboxyl-modified iron ion-imprinted PA66 resin Take 2.5g of the acrylic-modified iron-imprinted PA66 resin prepared in Example 4 and place it in a 50 mL sample bottle. Add 50 mL of the photoresist solution to be purified and place it in a constant temperature shaker (25℃, 100 rpm) for 300 min. Then take a sample, filter it through a filter membrane, and test the metal ion concentration in ICP-MS. The ICP-MS test results are shown in Table 4. The acrylic-modified iron-imprinted PA66 resin has excellent adsorption effect on iron ions, which is significantly better than that of the unmodified PA66 resin granules, and can reduce the metal ion content in the photoresist to the ppb level.
[0068] Table 4
[0069] Example 12: Removal of metal ions from photoresist using carboxyl-modified iron and calcium mixed ion-imprinted PA66 resin 2.5 g of the acrylic-modified iron and calcium mixed ion-imprinted PA66 resin prepared in Example 5 was placed in a 50 mL sample bottle, and 50 mL of the photoresist solution to be purified was added. The bottle was then placed in a constant temperature shaker (25℃, 100 rpm) and shaken for 300 min. A sample was then taken, filtered through a filter membrane, and the metal ion concentration was measured using ICP-MS. The ICP-MS test results are shown in Table 5. The acrylic-modified iron and calcium ion-imprinted PA66 resin exhibits excellent adsorption performance for iron and calcium ions, significantly better than the unmodified PA66 resin granules, and can reduce the metal ion content in the photoresist to the ppb level.
[0070] Table 5
[0071] Example 13: Removal of metal ions from photoresist using carboxyl-modified magnesium and calcium mixed ion-imprinted PA66 resin 2.5 g of the acrylic-modified magnesium and calcium mixed ion-imprinted PA66 resin prepared in Example 6 was placed in a 50 mL sample bottle, and 50 mL of the photoresist solution to be purified was added. The bottle was then placed in a constant temperature shaker (25℃, 100 rpm) and shaken for 300 min. A sample was then taken, filtered through a filter membrane, and the metal ion concentration was measured using ICP-MS. The ICP-MS test results are shown in Table 6. The acrylic-modified magnesium and calcium ion-imprinted PA66 resin exhibits excellent adsorption performance for magnesium and calcium ions, significantly better than the unmodified PA66 resin granules, and can reduce the metal ion content in the photoresist to the ppb level.
[0072] Table 6
[0073] Example 14: Removal of metal ions from photoresist using carboxyl-modified manganese, copper, and calcium mixed ion-imprinted PA66 resin. Take 2.5g of the acrylic-modified manganese, copper, and calcium mixed ion-imprinted PA66 resin prepared in Example 7 and place it in a 50 mL sample bottle. Add 50 mL of the photoresist solution to be purified and place the bottle in a constant temperature shaker (25℃, 100 rpm) and shake for 300 min. Then take a sample, filter it through a filter membrane, and test the metal ion concentration using ICP-MS. The ICP-MS test results are shown in Table 7. The acrylic-modified manganese, copper, and calcium ion-imprinted PA66 resin has excellent adsorption effect on manganese, copper, and calcium ions, which is significantly better than that of the unmodified PA66 resin granules. It can reduce the metal ion content in the photoresist to the ppb level.
[0074] Table 7
[0075] Example 15: Removal of metal ions from photoresist using carboxyl-modified iron, magnesium, and calcium mixed ion-imprinted PA66 resin. 2.5 g of the acrylic-modified iron, magnesium, and calcium mixed ion-imprinted PA66 resin prepared in Example 8 was placed in a 50 mL sample bottle, and 50 mL of the photoresist solution to be purified was added. The bottle was then placed in a constant temperature shaker (25℃, 100 rpm) and shaken for 300 min. A sample was then taken, filtered through a filter membrane, and the metal ion concentration was measured using ICP-MS. The ICP-MS test results are shown in Table 8. The acrylic-modified iron, magnesium, and calcium ion-imprinted PA66 resin exhibits excellent adsorption effects for iron, magnesium, and calcium ions, significantly better than the unmodified PA66 resin granules, and can reduce the metal ion content in the photoresist to the ppb level.
[0076] Table 8
[0077] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.
Claims
1. A method for preparing modified polyamide resin based on ion imprinting technology, characterized in that, Includes the following steps: (1) Disperse PA66 resin in water, add initiator and dispersant, shake vigorously, continue to add functional monomer to obtain reaction solution, and stir the reaction under closed conditions; wherein, the functional monomer is a monomer containing carboxyl group and unsaturated double bond; (2) After the reaction is complete, water is added to the reaction solution to separate the solid and liquid. The separated solid is activated with an activator, washed, and dried to obtain carboxyl-modified PA66 resin. (3) Add dispersant and metal ion template solution to carboxyl-modified PA66 resin, stir evenly, add excess deionized water to quench the reaction, stir vigorously and let stand, precipitate, separate solid and liquid, soak the separated solid with eluent, wash, then soak the solid with activator, wash, dry, and obtain carboxyl-modified metal ion imprinted PA66 resin.
2. The preparation method according to claim 1, characterized in that, The functional monomer is selected from one or more of acrylic acid, methacrylic acid, 4-pentenoic acid, itaconic acid, butenoic acid, and maleic acid; Preferably, the concentration of the functional monomer in the reaction solution is 2-4 mol / L.
3. The preparation method according to claim 1, characterized in that, The initiator is selected from one or more of benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxide, ammonium persulfate, isopropyl hydroperoxide, diisopropylbenzene hydroperoxide, and tert-butanol peroxide; Preferably, the amount of initiator added is 10-20% of the mass of PA66 resin.
4. The preparation method according to claim 1, characterized in that, The dispersant is selected from one or more of Tween 80, Tween 20, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.
5. The preparation method according to claim 1, characterized in that, The reaction temperature in step (1) is 383-403K and the reaction time is 6-10h.
6. The preparation method according to claim 1, characterized in that, The activator is selected from tetramethylammonium hydroxide with a concentration of 5-10%; The eluent is selected from a dilute acid solution with a concentration of 5-10%.
7. The preparation method according to claim 1, characterized in that, The metal ion template solution is a mixed solution prepared from metal salt, water and ethanol; Preferably, the metal salt has a molar concentration of 3.0-5.0 mol / kg in the metal ion template solution; Preferably, the metal ions contained in the metal ion template solution are selected from Ca... 2+ Fe 3+ Mg 2+ Mn 2+ Cu 2+ Li + Na + K + Cr 3+ Ni 2+ One or more of the following; Preferably, the volume ratio of water to ethanol in the metal ion template solution is 1.8:1-4:1; Preferably, the mass-to-volume ratio of carboxyl-modified PA66 resin to metal ion template solution is 1 g / 5-20 ml.
8. A modified polyamide resin based on ion imprinting technology, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. A method for removing metal ions from photoresist, characterized in that, Includes the following steps: The modified polyamide resin of claim 8 is mixed with a solution containing photoresist resin, and the mixture is shaken at a constant temperature. After the shaking is completed, the mixture is filtered to remove metal ions from the photoresist resin. The photoresist resin treated by the above method has a single metal ion content reduced to below 5 ppb.
10. The processing method according to claim 9, characterized in that, Each 2.5g of the modified polyamide resin corresponds to the purification of 10-200mL of a solution containing photoresist resin with a metal ion concentration greater than 50ppb and less than 300ppb. Preferably, the metal ion is selected from Li + Na + Mg 2+ A1 3+ K + Ca 2+ Cr 3+ Mn 2+ Fe 3+ Ni 2+ Cu 2+ and Sn 2+ One or more of the following; Preferably, the temperature for isothermal oscillation is room temperature, the isothermal oscillation time is 180-500 min, and the oscillation speed is 100-200 rpm.