CN113956392B - Photoresist resin and preparation method thereof - Google Patents
Photoresist resin and preparation method thereof Download PDFInfo
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- CN113956392B CN113956392B CN202111345050.XA CN202111345050A CN113956392B CN 113956392 B CN113956392 B CN 113956392B CN 202111345050 A CN202111345050 A CN 202111345050A CN 113956392 B CN113956392 B CN 113956392B
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- 239000011347 resin Substances 0.000 title claims abstract description 120
- 229920005989 resin Polymers 0.000 title claims abstract description 120
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 237
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 238000003756 stirring Methods 0.000 claims abstract description 81
- 239000002904 solvent Substances 0.000 claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000001301 oxygen Substances 0.000 claims abstract description 58
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 58
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 55
- 238000001035 drying Methods 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 238000001556 precipitation Methods 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 56
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 56
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 claims description 30
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 29
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- IFDUTQGPGFEDHJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolan-2-one Chemical compound CC(=C)C(O)=O.O=C1CCCO1 IFDUTQGPGFEDHJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 28
- 239000007788 liquid Substances 0.000 description 27
- 238000005303 weighing Methods 0.000 description 26
- QSUJHKWXLIQKEY-UHFFFAOYSA-N (2-oxooxolan-3-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCOC1=O QSUJHKWXLIQKEY-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention is applicable to the technical field of photoresist and provides photoresist resin and a preparation method thereof. The method comprises the following steps: placing a photoresist resin monomer and an initiator into a solvent for dissolution to obtain a monomer solution; placing the monomer solution in a nitrogen environment, and heating the monomer solution at a high temperature under a stirring state until the temperature of the monomer solution is higher than 100 ℃; introducing oxygen to promote the polymerization reaction of the photoresist resin monomer to obtain a reaction solution; and cooling the reaction liquid, and performing precipitation, separation and drying treatment to obtain the photoresist resin. In the process of preparing the photoresist resin, oxygen is introduced under the high temperature condition and forms a peroxy bond with the photoresist resin monomer, so that new free radicals are formed by breaking at high temperature, the polymerization speed of the photoresist resin monomer is further increased, the polymerization time is shortened, and the yield of the photoresist resin is improved.
Description
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to photoresist resin and a preparation method thereof.
Background
The photoresist is a mixed liquid which can be crosslinked or photolyzed in an exposure area after being exposed by exposure light sources with different wavelengths, so that the physical properties of the photoresist in a developing solution, particularly the solubility or the hydrophilicity and hydrophobicity of the photoresist are changed. The photoresist is mainly located at the upstream of the integrated circuit industry chain, and the micro-scale or nano-scale pattern is processed through etching or ion implantation and other processes. The photoresist mainly comprises film forming resin, a photosensitive agent, an additive, a solvent and the like, wherein the film forming resin directly determines the comprehensive performance of the photoresist and is a framework component of the photoresist.
In the process of polymerizing the photoresist resin monomer into the film-forming resin in the prior art, an initiator is usually added and polymerization reaction conditions are controlled to complete the polymerization reaction of the photoresist resin monomer so as to obtain the film-forming resin, but the yield of the film-forming resin prepared by the method is lower, the polymerization reaction time is longer, and the production cost is greatly increased.
Disclosure of Invention
The embodiment of the invention provides a photoresist resin and a preparation method thereof, aiming at solving the technical problems of lower yield and longer polymerization time of the photoresist resin in the prior art.
The embodiment of the invention is realized in such a way that the preparation method of the photoresist resin is characterized by comprising the following steps:
s1, placing a photoresist resin monomer and an initiator into a solvent for dissolution to obtain a monomer solution;
s2, placing the monomer solution in a nitrogen environment, and heating the monomer solution at a high temperature in a stirring state until the temperature of the monomer solution is higher than 100 ℃;
s3, introducing oxygen to promote the polymerization reaction of the photoresist resin monomer to obtain a reaction solution;
and S4, cooling the reaction liquid, and performing precipitation, separation and drying treatment to obtain the photoresist resin.
Further, in the method for preparing a photoresist resin, the photoresist resin monomer is a methacrylic monomer.
Further, in the method for preparing the photoresist resin, the photoresist resin monomer is one or more of methyl methacrylate monomer, methacrylic acid butyrolactone monomer and 2-methyl-2-adamantyl methacrylate monomer.
Further, in the method for producing a resist resin, the resist resin monomer is composed of methyl methacrylate monomer, butyrolactone methacrylate monomer, 2-methyl-2-adamantyl methacrylate monomer in a mass ratio of (1-10): (1-10): (1-10) and mixing.
Further, in the preparation method of the photoresist resin, the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile and dimethyl azodiisobutyrate.
Further, in the preparation method of the photoresist resin, the solvent is one or more of butyl acetate, DMF, toluene and propylene glycol methyl ether acetate.
Further, in the method for preparing a photoresist resin, the solvent is used in an amount of 4 to 10 times the mass of the photoresist resin monomer.
Further, in the method for preparing a photoresist resin, the initiator is used in an amount of 0.1 to 1wt% based on the mass of the photoresist resin monomer.
Further, in the method for preparing a photoresist resin, the polymerization time in the step S3 is 8-12 hours.
The embodiment of the invention also provides a photoresist resin, which is prepared by the preparation method of the photoresist resin.
The embodiment of the invention provides a photoresist resin and a preparation method thereof, wherein the method comprises the following steps: and (3) placing the photoresist resin monomer and the initiator in a solvent for dissolution, placing the obtained monomer solution in a nitrogen environment, heating the monomer solution at a high temperature under a stirring state until the temperature of the monomer solution is higher than 100 ℃, introducing oxygen to promote the polymerization reaction of the photoresist resin monomer, cooling the reaction solution after the reaction is finished, and performing precipitation, separation and drying treatment to obtain the photoresist resin. In the process of preparing the photoresist resin, oxygen is introduced under the high temperature condition and forms a peroxy bond with the photoresist resin monomer, so that new free radicals are formed by breaking at high temperature, the polymerization speed of the photoresist resin monomer is further increased, the polymerization time is shortened, and the yield of the photoresist resin is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the polymerization process of the photoresist resin, the oxygen and the monomer in the monomer solution form a peroxy bond, and the polymerization of the monomer has the advantages of high reaction rate, low system viscosity and easy control of molecular weight, and meanwhile, the peroxy bond formed by the oxygen and the monomer is very unstable and can be thermally decomposed to form a free radical with an initiating effect, so that the free radical polymerization reaction of the monomer is promoted, the polymerization time is shortened, and the yield of the photoresist resin is improved.
In the preparation method of the photoresist resin, the photoresist resin monomer is one or more of methyl methacrylate monomer, methacrylic acid butyrolactone monomer and 2-methyl-2-adamantyl methacrylate monomer.
Preferably, the photoresist resin monomer consists of methyl acrylate monomer, methacrylic acid butyrolactone monomer and 2-methyl-2-adamantyl methacrylate monomer in a mass ratio of (1-10): (1-10): (1-10) and mixing. The invention controls the mass ratio of methyl methacrylate monomer, methacrylic acid butyrolactone monomer and 2-methyl-2-adamantyl methacrylate monomer to (1-10): (1-10): (1-10), thereby further improving the yield of the photoresist resin while reducing the production of by-products during the polymerization reaction.
In the preparation method of the photoresist resin, the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile and dimethyl azodiisobutyrate, the solvent is one or more of butyl acetate, DMF, toluene and propylene glycol methyl ether acetate, the dosage of the solvent is 4-10 times of the mass of the photoresist resin monomer, and the dosage of the initiator is 0.1-1wt% of the mass of the photoresist resin monomer; the polymerization reaction time in the step S3 is 8-12h. Wherein, the initiator is preferably dimethyl azodiisobutyrate, and the solvent is preferably butyl acetate.
Example 1
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 0.1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 2
S1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.5wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 0.1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 3
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 0.1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 4
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 0.5MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 5
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.5wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 0.5MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 6
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 0.5MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 7
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 8
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.5wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 9
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 10
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 90 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 11
A method for preparing photoresist resin, comprising the steps of:
s1, placing 10 parts by weight of methyl methacrylate into a four-neck flask containing a butyl acetate solvent, stirring until the mixture is uniform, wherein the total usage amount of the butyl acetate solvent for dissolving monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 12
A method for preparing photoresist resin, comprising the steps of:
s1, placing 10 parts by weight of methacrylic acid butyrolactone in a four-neck flask containing a butyl acetate solvent, stirring until the mixture is uniform, wherein the total usage amount of the butyl acetate solvent for dissolving monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 13
A method for preparing photoresist resin, comprising the steps of:
s1, placing 10 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the mixture is uniform, wherein the total usage amount of the butyl acetate solvent for dissolving monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 14
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 8 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 15
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 12 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 16
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 100 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 17
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 130 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 18
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 4 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 19
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 10 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 20
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 8 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 21
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 12 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Example 22
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 120 ℃;
s3, introducing oxygen into the reaction container and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa;
s4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Comparative example 1
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, stirring and heating to 126 ℃ and carrying out polymerization reaction for 10 hours to obtain a reaction solution;
s3, cooling the reaction liquid, pouring the reaction liquid into n-hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Comparative example 2
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 0.5wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, stirring and heating to 126 ℃ and carrying out polymerization reaction for 10 hours to obtain a reaction solution;
s3, cooling the reaction liquid, pouring the reaction liquid into n-hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Comparative example 3
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing butyl acetate solvent, stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers, adding dimethyl azodiisobutyrate after the monomers are dissolved, and stirring until the monomers are dissolved to obtain a monomer solution, wherein the usage amount of an initiator is 1wt% of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, stirring and heating to 126 ℃ and carrying out polymerization reaction for 10 hours to obtain a reaction solution;
s3, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, weighing the photoresist resin after solid-liquid separation, and testing GPC.
Comparative example 4
A method for preparing photoresist resin, comprising the steps of:
s1, placing 3 parts by weight of methyl methacrylate, 2 parts by weight of butyrolactone methacrylate and 5 parts by weight of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a butyl acetate solvent, and stirring until the monomers are uniformly mixed, wherein the total usage amount of the butyl acetate solvent for dissolving the monomers is 6 times of the total mass of the monomers;
s2, replacing air of the reaction container with nitrogen, and stirring and heating to 126 ℃;
s3, introducing oxygen into the reaction vessel and performing polymerization reaction for 10 hours to obtain a reaction solution, wherein the oxygen pressure is 1MPa
S4, cooling the reaction liquid, pouring the reaction liquid into normal hexane for precipitation treatment, performing solid-liquid separation, drying under the condition of 0.09MPa of vacuum degree, weighing the photoresist resin after the drying is finished, and testing GPC.
Test case
The photoresist resins prepared in examples 1 to 9 and comparative examples 1 to 4 were evaluated for yield, weight average molecular weight and PDI, and the test results are shown in Table 1:
TABLE 1 polymerization results
As can be seen from Table 1, under the high temperature reaction, the oxygen-free condition, the chain termination reaction increases due to the rapid decomposition of the initiator at high temperature, the polymer chain is short, and the more by-products are more apparent, especially when the amount of the initiator is larger.
Meanwhile, under the high-temperature condition and the aerobic condition, the polymerization of the monomer can be promoted, the higher the oxygen content is, the longer the polymer chain is, namely, more peroxide bonds are broken, new active free radicals are formed, the polymerization reaction is continued, and then the long-chain polymer is formed, the molecular weight of the photoresist resin is large, the molecular weight distribution is narrow, and meanwhile, under the condition of only oxygen, the induction of a pre-initiator is absent, the polymer chain is shorter, but compared with the traditional reaction, the reaction is promoted.
In summary, in the high-temperature polymerization reaction, oxygen is introduced into the polymerization monomer to promote the polymerization reaction, and as the pressure of oxygen increases, the reaction is faster, and the initiator is required to assist at a low temperature in the early stage of polymerization.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. A method for preparing photoresist resin, comprising the steps of:
s1, placing a photoresist resin monomer and an initiator into a solvent for dissolution to obtain a monomer solution;
s2, placing the monomer solution in a nitrogen environment, and heating the monomer solution at a high temperature in a stirring state until the temperature of the monomer solution is higher than 100 ℃;
s3, introducing oxygen to promote the polymerization reaction of the photoresist resin monomer to obtain a reaction solution;
s4, cooling the reaction liquid, and performing precipitation, separation and drying treatment to obtain photoresist resin;
wherein the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile and dimethyl azodiisobutyrate; the photoresist resin monomer is prepared from methyl methacrylate monomer, methacrylic acid butyrolactone monomer and 2-methyl-2-adamantyl methacrylate monomer according to the mass ratio of (1-10): (1-10): (1-10) and mixing.
2. The method of claim 1, wherein the solvent is one or more of butyl acetate, DMF, toluene, propylene glycol methyl ether acetate.
3. The method of producing a resist resin according to claim 1, wherein the solvent is used in an amount of 4 to 10 times the mass of the resist resin monomer.
4. The method of producing a resist resin according to claim 1, wherein the initiator is used in an amount of 0.1 to 1% by weight based on the mass of the resist resin monomer.
5. The method of producing a photoresist resin according to claim 1, wherein the polymerization time in step S3 is 8 to 12 hours.
6. A photoresist resin prepared by the method of any one of claims 1 to 5.
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