Acrylic resin polymers, methods of making and using the same

Abstract

This invention discloses an acrylic resin polymer, its preparation method, and its application. The acrylic resin polymer has a structure as shown in formula (I): where x = 1–1600; R1 is selected from residues of diols or bisphenols, triols or bisphenols, or tetraols or bisphenols, n ≥ 2; R2 is selected from residues of diols or bisphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine or chlorine atoms; R5 is selected from any one of benzyl, adamantyl or hydroxylated adamantyl, C1–C12 alkyl or hydroxylated C1–C12 alkyl, or glycidyl. This invention provides a polymer with main chain induced cleavage and a two-arm, three-arm, or four-arm topological structure. This structural design feature is beneficial for improving the photolithography sensitivity of the resin.

Description

Technical Field

[0001] This invention belongs to the field of polymer preparation technology, specifically relating to an acrylic resin polymer, its preparation method, and its application. Background Technology

[0002] The molecular weight and molecular weight distribution of polymers are important indicators for resins in practical applications. In photoresists, the molecular weight of the polymer determines the performance of the photoresist. In the development process of positive photoresists, the solubility change of methacrylic acid resins in the developer is mostly achieved through the breaking of chemical bonds in the side chain groups. During this process, the photoresist requires the polymer to have a certain molecular weight to obtain fine patterns. Since the main chain length (degree of polymerization) of the polymer does not change before and after photolithography, the side chain groups of the polymer need to have high photolithographic response sensitivity and generate sufficient hydrophilic groups to achieve polymer dissolution in the developer. However, the number of chemical bonds broken by a constant exposure dose is limited. To meet the change in photoresist solubility, the exposure energy must be increased, which increases the requirements of the photolithography machine. At the same time, an excessively long polymer main chain can also lead to an increase in pattern edge roughness. Therefore, to avoid the adverse effects of changes in resin solubility before and after photolithography, the molecular weight of the polymer needs to be controlled within a narrow window.

[0003] In summary, the main chain length (degree of polymerization) of traditional polymers remains unchanged before and after photolithography, which to some extent affects the photolithography sensitivity and the roughness of the pattern edge. Summary of the Invention

[0004] The main objective of this invention is to provide an acrylic resin polymer, its preparation method, and its application, in order to overcome the shortcomings of the prior art.

[0005] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0006] This invention provides an acrylic resin polymer having a structure as shown in formula (I):

[0007]

[0008] Wherein, x = 1 to 1600; R1 is selected from residues of diols or diphenols, residues of triols or triphenols, residues of tetraols or tetraphenols, and n ≥ 2; R2 is selected from residues of diols or diphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine atoms or chlorine atoms; R5 is selected from any one of benzyl, adamantyl or hydroxy-substituted adamantyl, C1-C12 alkyl or hydroxy-substituted C1-C12 alkyl, and glycidyl.

[0009] The acrylic resin polymer has a molecular weight of 1,000 to 200,000 g / mol and a molecular weight distribution of 1.04 to 2.50.

[0010] Preferably, R1 is selected from residues of diols or diphenols, and n is 2; or, R1 is selected from residues of triols or triphenols, and n is 3; or, R1 is selected from residues of tetraols or tetraphenols, and n is 4.

[0011] The present invention also provides a method for preparing the aforementioned acrylic resin polymer, comprising:

[0012] In an inert gas atmosphere, acrylate monomers or methacrylate monomers, halogen initiators, catalysts, and ligands are subjected to a reversible-deactivated free radical polymerization reaction catalyzed by metals or metal salts in a solvent at 0–110°C to obtain the acrylate resin polymer.

[0013] The halogen initiator has a structure as shown in formula (II):

[0014]

[0015] R1 is selected from residues of diols or diphenols, triols or triphenols, or tetraols or tetraphenols, n≥2; R2 is selected from residues of diols or diphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine or chlorine atoms.

[0016] Preferably, R1 is selected from residues of diols or diphenols, and n is 2; or, R1 is selected from residues of triols or triphenols, and n is 3; or, R1 is selected from residues of tetraols or tetraphenols, and n is 4.

[0017] Furthermore, the molar ratio of the acrylate monomer or methacrylate monomer, halogen initiator, catalyst and ligand is (1-1600):1:(0.05-10):(0.15-15).

[0018] The present invention also provides the application of the aforementioned acrylic resin polymers in the preparation of photoresists.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The acrylic resin polymer of the present invention is a polymer with main chain stimulation and fracture, and the topology is two-armed, three-armed or four-armed. This structural design feature is beneficial to improving the photolithography sensitivity of the resin.

[0021] (2) This invention utilizes a reversible-deactivated free radical polymerization method catalyzed by metal or metal salt, and designs and synthesizes halogen-containing compounds with acetal structures as initiators for free radical polymerization to achieve the synthesis of polymer resins containing acetal groups in the polymer backbone. A methacrylic acid resin with acetal groups in the backbone is prepared. The molecular weight of the resin is controllable and the molecular weight distribution is relatively narrow (Mw / Mn < 1.50), which meets the characteristics of "living" free radical polymerization. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 It is ethyl 2-vinyloxy-2-bromo-2-methylpropionate in one embodiment of this application. 1 Figure of H NMR test results.

[0024] Figure 2 It is the bifunctional halogen initiator (II-12) in one embodiment of this application. 1 Figure of H NMR test results.

[0025] Figure 3 It is the trifunctional halogen initiator (II-13) in one embodiment of this application. 1 Figure of H NMR test results.

[0026] Figure 4 It is the tetrafunctional halogen initiator (I1-22) in one embodiment of this application. 1 Figure of H NMR test results.

[0027] Figure 5 These are photolithographic results of methacrylic resin in Examples 5, 6 and Comparative Example 1 of this application (the mask line width used is 200 nanometers). Detailed Implementation

[0028] In view of the deficiencies of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention. The technical solution of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0029] One aspect of this invention provides an acrylic resin polymer having a structure as shown in formula (I):

[0030]

[0031] Wherein, x = 1 to 1600; R1 is selected from residues of diols or diphenols, residues of triols or triphenols, residues of tetraols or tetraphenols, and n ≥ 2; R2 is selected from residues of diols or diphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine atoms or chlorine atoms; R5 is selected from any one of benzyl, adamantyl or hydroxy-substituted adamantyl, C1-C12 alkyl or hydroxy-substituted C1-C12 alkyl, and glycidyl.

[0032] The acrylic resin polymer has a molecular weight of 1,000 to 200,000 g / mol and a molecular weight distribution of 1.04 to 2.50.

[0033] Preferably, R1 is selected from residues of diols or diphenols, and n is 2; or, R1 is selected from residues of triols or triphenols, and n is 3; or, R1 is selected from residues of tetraols or tetraphenols, and n is 4.

[0034] Another aspect of the present invention provides a method for preparing the aforementioned acrylic resin polymer, comprising:

[0035] In an inert gas atmosphere, acrylate monomers or methacrylate monomers, halogen initiators, catalysts, and ligands are subjected to a reversible-deactivated free radical polymerization reaction catalyzed by metals or metal salts in a solvent at 0–110°C to obtain the acrylate resin polymer.

[0036] The halogen initiator has a structure as shown in formula (II):

[0037]

[0038] R1 is selected from residues of diols or diphenols, triols or triphenols, or tetraols or tetraphenols, n≥2; R2 is selected from residues of diols or diphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine or chlorine atoms.

[0039] Preferably, R1 is selected from residues of diols or diphenols, and n is 2; or, R1 is selected from residues of triols or triphenols, and n is 3; or, R1 is selected from residues of tetraols or tetraphenols, and n is 4.

[0040] In some preferred embodiments, the molar ratio of the acrylate monomer or methacrylate monomer, halogen initiator, catalyst and ligand is (1-1600):1:(0.05-10):(0.15-15).

[0041] In some more preferred embodiments, the molar ratio of the acrylate monomer or methacrylate monomer, halogen initiator, catalyst and ligand is (20-75):1:(1-5):(2-6).

[0042] In some preferred embodiments, the acrylate monomer or methacrylate monomer may be selected from benzyl methacrylate (BzMA), methyl methacrylate (MMA), tert-butyl methacrylate (tBMA), glycidyl methacrylate (GMA), n-butyl methacrylate (nBMA), dicyclopentyl methacrylate (HDCPMA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), 2-methyl-2-adamantyl methacrylate (MAMA), 2-ethyl-2-adamantyl methacrylate (EAMA), and 1-adamantyl methacrylate. The ester (ADAMA), 3-hydroxy-1-adamantyl methacrylate (HAMA), benzyl acrylate (BzA), methyl acrylate (MA), tert-butyl acrylate (tBA), glycidyl acrylate (GA), n-butyl acrylate (nBA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 2-methyl-2-adamantyl acrylate (MAA), 2-ethyl-2-adamantyl acrylate (EAA), 1-adamantyl acrylate (ADAA), 3-hydroxy-1-adamantyl acrylate (HAA), etc., are any one or more combinations thereof, but are not limited thereto.

[0043] In some more preferred embodiments, the methacrylate monomer is a homopolymer or copolymer of one or more of the following monomers: tert-butyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl methacrylate, and 3-hydroxy-1-adamantyl methacrylate.

[0044] In some preferred embodiments, the diol or diphenol may be selected from any one or more of the following structures:

[0045]

[0046] In some preferred embodiments, the triol or triphenol may be selected from any one or more of the following structures:

[0047]

[0048] In some preferred embodiments, the tetraol or tetraphenol may be selected from any one or more of the following structures:

[0049]

[0050] In some preferred embodiments, the halogen initiator is selected from one or more compounds of formulas II-1 to II-24:

[0051]

[0052] In some preferred embodiments, the catalyst may include any one or more of copper, iron, cupric chloride, cuprous chloride, ferric bromide, ferrous bromide, cupric bromide, cuprous bromide, etc., but is not limited thereto.

[0053] In some more preferred embodiments, the catalyst is cuprous bromide.

[0054] In some preferred embodiments, the ligand may include, but is not limited to, any one or more of N,N,N′,N,′N″-pentamethyldiethylenetriamine (PMDETA), 2,2′-bipyridine (BIPY), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA).

[0055] In some more preferred embodiments, the ligand is N,N,N′,N,′N″-pentamethyldiethylenetriamine.

[0056] In some preferred embodiments, the solvent may include any one or more of toluene, xylene, tetrahydrofuran, dioxane, ethyl acetate, etc., but is not limited thereto.

[0057] In some more preferred embodiments, the solvent is toluene.

[0058] Furthermore, when the methacrylate monomers are copolymerized, the molar ratio of tert-butyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl methacrylate and 3-hydroxy-1-adamantyl methacrylate is (3-400):(3-400):(3-400):(3-400).

[0059] Furthermore, the molar ratio of tert-butyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl methacrylate and 3-hydroxy-1-adamantyl methacrylate is (5-40):(5-40):(5-40):(5-40).

[0060] In a more specific implementation, the methacrylate monomers are copolymerized from tert-butyl methacrylate, 2-methyl-2-adamantyl methacrylate, and 3-hydroxy-1-adamantyl methacrylate. The halogen initiator is compound II-13, the catalyst is cuprous bromide, and the ligand is N,N,N′,N,′N″-pentamethyldiethylenetriamine. A reversible-deactivated free radical polymerization reaction catalyzed by a metal or metal salt is carried out in toluene at 90°C for 24 hours, achieving a monomer conversion rate of >50%. The structural formula of the obtained polymer is as follows:

[0061]

[0062] By means of the above-described solution, the resin of the present invention has at least the following advantages:

[0063] This invention utilizes a reversible-deactivated free radical polymerization method catalyzed by metals or metal salts to prepare methacrylic acid resin with acetal groups in the main chain. The molecular weight of this resin is controllable, and the molecular weight distribution is relatively narrow (Mw / Mn < 1.50), which conforms to the characteristics of "living" free radical polymerization.

[0064] Another aspect of the present invention provides the application of the aforementioned methacrylic resin polymer in the preparation of photoresists.

[0065] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0066] Unless otherwise specified, the raw materials and reagents used in the following embodiments of the present invention can be obtained commercially and used directly.

[0067] The following test method is used in this invention:

[0068] 1. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained polymers were determined by a TOSOH HLC-8420 gel permeation chromatograph equipped with a refractive index detector (TOSOH). The guard column used was a TSK gel Super MP-N (4.6 × 20 mm). The detection column was a TSK gel Super HZ-N (4.6 × 150 mm). DMF (with 0.1 wt% LiBr added as a co-solvent) was used as the eluent. The test temperature was 40 °C, and the flow rate was 0.35 mL·min. -1 The molecular weight range is 5×10 2 ~5×10 5g / mol. Gel permeation chromatography samples were injected using a TOSOH plus autosampler, and the results for the polymer were calibrated using standard PS samples purchased from TOSOH. The sample preparation procedure for GPC testing was as follows: the polymer was dissolved in THF at a concentration of 1–5 mg / mL. The polymer solution was passed through a small column of neutral alumina and a syringe fitted with a 0.45 μm filter. Finally, the purified polymer solution was injected into the test vial.

[0069] 2. The NMR spectra of the obtained products and polymers were obtained by Bruker 400MHz NMR spectrometer, using DMSO-d6 as the deuterated reagent, at 25℃, with tetramethylsilane (TMS) as the internal standard.

[0070] Example 12 Synthesis of ethyl vinyloxy-2-bromo-2-methylpropionate

[0071] Under an inert gas atmosphere, vinyl glycol ether (4.00 g, 45.4 mmol) was dissolved in 100 mL of anhydrous dichloromethane, and triethylamine (7.56 mL, 54.4 mmol) was added. The mixture was stirred on a magnetic stirrer, and the reaction vessel was placed in an ice bath. Then, a mixture of bromoisobutyryl bromide (5.62 mL, 45.4 mmol) and anhydrous dichloromethane (20 mL) was added dropwise. After the addition was complete, the reaction was continued at room temperature with stirring for at least 8 hours. After the reaction was complete, the product was extracted, dried, the solvent was evaporated, and purified to obtain a pale yellow transparent liquid, namely ethyl 2-vinyloxy-2-bromo-2-methylpropionate, in a total of 2.13 g, with a yield of 86%. The ethyl 2-vinyloxy-2-bromo-2-methylpropionate... 1 H NMR test results, such as Figure 1 As shown, the compound ethyl 2-vinyloxy-2-bromo-2-methylpropionate was successfully synthesized with a purity >95%.

[0072] The molecular structural formula of ethyl 2-vinyloxy-2-bromo-2-methylpropionate in this embodiment is as follows:

[0073]

[0074] Example 2 Synthesis of a bifunctional halogen initiator (II-12)

[0075] Under an inert atmosphere, bisphenol A (1.44 g, 6.3 mmol) and 50 mL of anhydrous dichloromethane were added to a reaction flask, followed by p-toluenesulfonic acid (54.3 mg, 0.3 mmol). Under ice bath conditions, a mixture of ethyl 2-vinyloxy-2-bromo-2-methylpropionate (3.00 g, 12.6 mmol) and 20 mL of anhydrous dichloromethane was added dropwise to the above reaction mixture. After the addition was complete, the reaction mixture was stirred at room temperature for at least 12 h. After the reaction was completed, the mixture was extracted, dried, the solvent was evaporated, and purified to obtain a pale yellow transparent liquid (3.68 g, yield 83%). This pale yellow transparent liquid was a bifunctional halogen initiator (II-12). 1 H NMR test results, such as Figure 2 As shown, the bifunctional halogen initiator (II-12) was successfully synthesized with a purity >95%.

[0076] The molecular structure of the bifunctional halogen initiator (II-12) in this embodiment is as follows:

[0077]

[0078] Example 3 Synthesis of a trifunctional halogen initiator (II-13)

[0079] Under an inert atmosphere, 1,1,1-tris(4-hydroxyphenyl)ethane (3.44 g, 11.2 mmol) and 30 mL of anhydrous dichloromethane were added to a reaction flask, followed by p-toluenesulfonic acid (56.0 mg, 0.6 mmol). Under ice bath conditions, a mixture of ethyl 2-vinyloxy-2-bromo-2-methylpropionate (8.00 g, 33.7 mmol) and 10 mL of anhydrous dichloromethane was added dropwise to the above reaction mixture. After the addition was complete, the reaction mixture was stirred at room temperature for at least 12 h. After the reaction was complete, the mixture was extracted, dried, the solvent was evaporated, and purified to obtain a pale yellow transparent liquid (7.88 g, yield 69%). This pale yellow transparent liquid was a trifunctional halogen initiator (II-13). 1 H NMR test results, such as Figure 3 As shown, the trifunctional halogen initiator (II-13) was successfully synthesized with a purity >95%.

[0080] The molecular structure of the trifunctional halogen initiator (II-13) in this embodiment is as follows:

[0081]

[0082] Example 4 Synthesis of a tetrafunctional halogen initiator (II-22)

[0083] Under an inert atmosphere, bis(trimethylol)propane (0.70 g, 2.8 mmol) and 30 mL of ethylene glycol dimethyl ether were added to a reaction flask, followed by p-toluenesulfonic acid (20 mg, 0.1 mmol). Ethyl 2-vinyloxy-2-bromo-2-methylpropionate (2.66 g, 11.2 mmol) was added directly to the reaction mixture under ice bath conditions. The reaction mixture was then stirred at room temperature for at least 12 h. After the reaction was complete, the mixture was extracted, dried, the solvent was evaporated, and purified to obtain a pale yellow transparent liquid (1.68 g, 50% yield). This pale yellow transparent liquid was a tetrafunctional halogen initiator (II-22). 1 HNMR test results, such as Figure 4 As shown, the tetrafunctional halogen initiator (II-22) was successfully synthesized with a purity >95%.

[0084] The molecular structure of the tetrafunctional halogen initiator (II-22) in this embodiment is as follows:

[0085]

[0086] Example 5: Preparation of Two-Arm Type Methacrylic Resin

[0087] A reversible-deactivated free radical polymerization catalyzed by a bifunctional halogen initiator (II-12) was carried out using metal or metal salt catalysis. The feed was added at a molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [II-12]0 / [CuBr]0 / [PMDETA]0 = 30 / 30 / 30 / 30 / 1 / 3 / 5, with tBMA (3.04 g, 21.4 mmol) and ADMA (4.70 g, 100 mmol ... 5.00 g (21.4 mmol), MAMA (5.00 g, 21.4 mmol), HAMA (5.05 g, 21.4 mmol), initiator II-12 (0.50 g, 0.7 mmol), CuBr (0.31 g, 2.1 mmol), and PMDETA (0.62 g, 3.6 mmol) were added to a dry 25 mL reaction flask equipped with a magnetic stir bar, and 10 mL of anhydrous toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere through a double-row tube, sealed, and placed in a magnetic stirrer at 90 °C for 24 h. After polymerization, the reaction mixture was removed, diluted with 20 mL of tetrahydrofuran, and precipitated with 500 mL of petroleum ether. The polymer product was collected by filtration and dried to constant weight under vacuum at 30 °C. The polymerization conversion was then calculated by gravimetric method.

[0088] The molecular structure of the two-arm methacrylic resin in this embodiment is as follows:

[0089]

[0090] Example 6: Preparation of Three-Arm Type Methacrylic Resin

[0091] A trifunctional halogen initiator (II-13) was used as the initiator for reversible-deactivated free radical polymerization catalyzed by metal or metal salt. The feed was added in a molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [I-13]0 / [CuBr]0 / [PMDETA]0 = 30 / 30 / 30 / 30 / 1 / 4 / 6, with tBMA (2.93 g, 20.60 mmol) and ADAMA (4.55 g) as the initiator. 20.60 mmol of HAMA (4.84 g, 20.60 mmol), 20.60 mmol of MAMA (4.88 g, 20.60 mmol), 0.70 g of initiator II-13 (0.70 g, 0.69 mmol), 0.39 g of CuBr (0.39 g, 2.74 mmol), and 0.72 g of PMDETA (4.12 mmol) were added to a 25 mL reaction flask equipped with a magnetic stir bar and dried. 10 mL of toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere using a double-row tube, and the flask was sealed and placed in a magnetic stirrer at 90 °C for 24 h. After polymerization, the reaction mixture was removed and precipitated using 500 mL of petroleum ether. The polymer product was collected by filtration and dried to constant weight under vacuum at 30 °C. The polymerization conversion was then calculated by gravimetric method.

[0092] The molecular structure of the three-arm methacrylic resin in this embodiment is as follows:

[0093]

[0094] Example 7 Preparation of a four-arm type methacrylic resin

[0095] A tetrafunctional halogen initiator (II-22) was used as the initiator for reversible-deactivated free radical polymerization catalyzed by metal or metal salt. The feed was added at a molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [II-22]0 / [CuBr]0 / [PMDETA]0 = 30 / 30 / 30 / 30 / 1 / 5 / 6, with tBMA (100.0 mg, 0.70 mmol) and ADAMA (154.9 mg, 0.70 mmol) as the initiator. The following reagents were added to a 5 mL reaction flask equipped with a magnetic stir bar and dried: g (0.70 mmol), MAMA (164.8 mg, 0.70 mmol), HAMA (166.2 mg, 0.70 mmol), initiator II-22 (28.1 mg, 0.02 mmol), CuBr (16.8 mg, 0.12 mmol), and PMDETA (24.3 mg, 0.14 mmol). 2 mL of toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere using a double-row tube, sealed, and placed in a magnetic stir bar at 90 °C for a set time. After polymerization, the reaction mixture was removed and precipitated using 200 mL of petroleum ether. The polymer product was collected by filtration and dried under vacuum at 30 °C to constant weight. The polymerization conversion was then calculated by gravimetric method.

[0096] The molecular structure of the four-armed methacrylic resin in this embodiment is as follows:

[0097]

[0098] Comparative Example 1: Preparation of Conventional Methacrylic Resin

[0099] Using ethyl 2-bromoisobutyrate (EBiB) as the initiator for reversible-deactivated free radical polymerization catalyzed by cuprous bromide, the prepared resin served as a comparative example, with a feed molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [EBiB]0 / [CuBr]0 / [PMD] [ETA]0 = 30 / 30 / 30 / 30 / 1 / 1 / 2, adding tBMA (3.04 g, 21.4 mmol), ADAMA (4.70 g, 21.4 mmol), MAMA (5.00 g, 21.4 mmol), HAMA (5.05 g, 21.4 mmol), EBiB (0.14 g, 0.7 mmol), CuBr (102.1 mg, 0.7 mmol), and PMDETA (0.25 g, 1.4 mmol) to a 25 mL reaction flask equipped with a magnetic stir bar and dried. 10 mL of toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere through a double-row tube, sealed, and placed in a magnetic stirrer at 90 °C for a set time. After polymerization, the reaction mixture was removed and precipitated using 500 mL of petroleum ether. The polymer product was collected by filtration and dried to constant weight under vacuum at 30 °C. The polymerization conversion was then calculated by gravimetric method.

[0100] The molecular structure of the bifunctional halogen initiator in this embodiment is as follows:

[0101]

[0102] Photolithography was performed using the methacrylic resins of Examples 5, 6, and Comparative Example 1, with a mask linewidth of 200 nanometers. The photolithography results are as follows: Figure 5 As shown, based on the exposure dose, the exposure sensitivity of the three resins is ranked as follows: three-arm methacrylic resin > two-arm methacrylic resin > conventional methacrylic resin (the smaller the exposure dose, the higher the exposure sensitivity).

[0103] Example 8: Preparation of Two-Arm Type Methacrylic Resin

[0104] A reversible-deactivated free radical polymerization catalyzed by a bifunctional halogen initiator (II-12) was carried out using metal or metal salt catalysis. The feed was added at a molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [II-12]0 / [CuBr]0 / [PMDETA]0 = 15 / 15 / 15 / 1 / 3 / 5, with tBMA (1.52 g, 10.7 mmol) and ADMA (2.35 g, 10.7 mmol) as the initiator. 0.50 g (10.7 mmol), MAMA (2.50 g, 10.7 mmol), HAMA (2.52 g, 10.7 mmol), initiator II-12 (0.50 g, 0.7 mmol), CuBr (0.31 g, 2.1 mmol), and PMDETA (0.62 g, 3.6 mmol) were added to a dry 25 mL reaction flask equipped with a magnetic stir bar, and 10 mL of anhydrous toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere through a double-row tube, sealed, and placed in a magnetic stirrer at 90 °C for 24 h. After polymerization, the reaction mixture was removed, diluted with 20 mL of tetrahydrofuran, and precipitated with 500 mL of petroleum ether. The polymer product was collected by filtration and dried to constant weight under vacuum at 30 °C. The polymerization conversion was then calculated by gravimetric method.

[0105] The molecular structure of the two-arm methacrylic resin in this embodiment is as follows:

[0106]

[0107] Example 9: Preparation of Three-Arm Type Methacrylic Resin

[0108] A trifunctional halogen initiator (II-13) was used as the initiator for reversible-deactivated free radical polymerization catalyzed by metal or metal salt. The feed was carried out at a molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [I-13]0 / [CuBr]0 / [PMDETA]0 = 15 / 15 / 15 / 1 / 4 / 6, with tBMA (1.87 g, 10.3 mmol) and ADAMA (2.28 g, 10.3 mmol) as the initiator. 10.3 mmol of HAMA (2.42 g, 10.3 mmol), 10.3 mmol of MAMA (2.44 g, 10.3 mmol), 10.3 mmol of HAMA (2.44 g, 10.3 mmol), 0.70 g of initiator II-13 (0.70 g, 0.69 mmol), 0.39 g of CuBr (0.39 g, 2.74 mmol), and 0.72 g of PMDETA (0.72 g, 4.12 mmol) were added to a 25 mL reaction flask equipped with a magnetic stir bar and dried. 10 mL of toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere using a double-row tube, and the flask was sealed and placed in a magnetic stirrer at 90°C for 24 h. After polymerization, the reaction mixture was removed and precipitated using 500 mL of petroleum ether. The polymer product was collected by filtration and dried to constant weight under vacuum at 30°C. The polymerization conversion was then calculated by gravimetric method.

[0109] The molecular structure of the three-arm methacrylic resin in this embodiment is as follows:

[0110]

[0111] Example 10 Preparation of a four-arm type methacrylic resin

[0112] A reversible-deactivated free radical polymerization catalyzed by a tetrafunctional halogen initiator (II-22) was carried out using metal or metal salt catalysis. The feed was added at a molar ratio of [tBMA]0 / [ADAMA]0 / [MAMA]0 / [HAMA]0 / [II-22]0 / [CuBr]0 / [PMDETA]0 = 15 / 15 / 15 / 15 / 5 / 6, with tBMA (100.0 mg, 0.70 mmol) and ADAMA (154.9 mg, 0.70 mmol) as the initiator. The following reagents were added to a 5 mL reaction flask equipped with a magnetic stir bar and dried: g (0.70 mmol), MAMA (164.8 mg, 0.70 mmol), HAMA (166.2 mg, 0.70 mmol), initiator II-22 (56.2 mg, 0.04 mmol), CuBr (33.6 mg, 0.24 mmol), and PMDETA (48.6 mg, 0.28 mmol). 2 mL of toluene was added as the polymerization solvent. The reaction atmosphere was then purged to an inert gas atmosphere using a double-row tube, sealed, and placed in a magnetic stirrer at 90 °C for a set time. After polymerization, the reaction mixture was removed and precipitated using 200 mL of petroleum ether. The polymer product was collected by filtration and dried under vacuum at 30 °C to constant weight. The polymerization conversion was then calculated by gravimetric method.

[0113] The molecular structure of the four-armed methacrylic resin in this embodiment is as follows:

[0114]

[0115] The synthesis data of methacrylic resin in Examples 5-10 and Comparative Example 1 are shown in the table below.

[0116]

[0117] Note: Yield was calculated by weighing; Mn and PDI were obtained by GPC testing.

[0118] As can be seen from the table above, the yield of the methacrylic resin prepared by this invention is greater than 50%, and polymer structures with different monomer ratios and molecular weights can be designed. The number-average molecular weight obtained by the test is greater than 5000 g / mol, and the molecular weight distribution is narrow, ranging from 1.20 to 1.50.

[0119] In this invention, the polymerizing monomers used can also be other (meth)acrylate monomers besides those in the above examples for homopolymerization or copolymerization, and the same or similar polymerization methods can be used to obtain the same results and conclusions.

[0120] In summary, the present invention provides a method for preparing a type of methacrylate polymer with a main chain containing an acetal structure. The invention introduces a type of halogen-containing compound as a free radical polymerization initiator, and uses a reversible-deactivated free radical polymerization method catalyzed by metal or metal salt to prepare a (meth)acrylic resin with a main chain containing an acetal group. The molecular weight of the resin is controllable and the molecular weight distribution is relatively narrow (Mw / Mn < 1.50), which meets the characteristics of "living" free radical polymerization.

[0121] This invention provides an application of the (meth)acrylic resin with acetal groups in the main chain described in the above technical solution in the field of photoresist.

[0122] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. Application of acrylic resin polymers in the preparation of photoresists, wherein the acrylic resin polymer has a structure as shown in formula (I): ； in, x = 1~1600; R1 is selected from residues of diols or bisphenols, residues of triols or bisphenols, residues of tetraols or tetraphenols, n≥2; R2 is selected from residues of diols or bisphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine atoms or chlorine atoms; R5 is selected from any one of benzyl, adamantyl or hydroxy-substituted adamantyl, C1~C12 alkyl or hydroxy-substituted C1~C12 alkyl, glycidyl; The acrylic resin polymer has a molecular weight of 1,000 to 200,000 g / mol and a molecular weight distribution of 1.04 to 2.

50.

2. The application according to claim 1, characterized in that: R1 is selected from residues of diols or diphenols, and n is 2; or R1 is selected from residues of triols or triphenols, and n is 3; or R1 is selected from residues of tetraols or tetraphenols, and n is 4.

3. The application according to claim 1, characterized in that, The preparation method of the acrylic resin polymer includes: In an inert gas atmosphere, acrylate monomers or methacrylate monomers, halogen initiators, catalysts, and coordinating agents are placed in a solvent at a temperature of 0–110 °C. o A reversible-deactivated free radical polymerization reaction catalyzed by metal or metal salt occurs at C to obtain the acrylic resin polymer described above. The halogen initiator has a structure as shown in formula (II): ； R1 is selected from residues of diols or diphenols, triols or triphenols, or tetraols or tetraphenols, n≥2; R2 is selected from residues of diols or diphenols; R3 is selected from methyl or hydrogen atoms; R4 is selected from halogen bromine or chlorine atoms.

4. The application according to claim 3, characterized in that: The molar ratio of the acrylate monomer or methacrylate monomer, halogen initiator, catalyst and ligand is (1~1600):1:(0.05~10):(0.15~15).

5. The application according to claim 3 or 4, characterized in that: The acrylate monomers or methacrylate monomers are selected from any one or more combinations of benzyl methacrylate, methyl methacrylate, tert-butyl methacrylate, glycidyl methacrylate, n-butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 1-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, benzyl acrylate, methyl acrylate, tert-butyl acrylate, glycidyl acrylate, n-butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl acrylate, and 3-hydroxy-1-adamantyl acrylate.

6. The application according to claim 3 or 4, characterized in that, The diol or diphenol is selected from any one or more of the following structures: 。 7. The application according to claim 3 or 4, characterized in that, The triol or triphenol is selected from any one or more of the following structures: 。 8. The application according to claim 3 or 4, characterized in that, The tetraol or tetraphenol is selected from any one or more of the following structures: 。 9. The application according to claim 6, characterized in that, The halogen initiator is selected from one or more of the compounds shown in Formula II-1 to Formula II-24: 。 10. The application according to claim 3 or 4, characterized in that: The catalyst includes any one or a combination of two or more of copper, iron, copper chloride, cuprous chloride, ferric bromide, ferrous bromide, copper bromide, and cuprous bromide.

11. The application according to claim 3 or 4, characterized in that: The ligand includes any one or a combination of two or more of N,N,N',N,'N''-pentamethyldiethylenetriamine, 2,2'-bipyridine, and 1,1,4,7,10,10-hexamethyltriethylenetetramine.

12. The application according to claim 3 or 4, characterized in that: The solvent includes any one or a combination of two or more of toluene, xylene, tetrahydrofuran, dioxane, and ethyl acetate.

Images