Acrylate polymer, and preparation method therefor and use thereof

Abstract

An acrylate polymer, and a preparation method therefor and the use thereof. The polymer comprises at least one repeat unit. The repeat unit has a structure represented by formula (I): (I), wherein Ar1 and Ar2 each independently comprise an aromatic group having 6-30 atoms in the ring thereof; R1, R2, R3 and R4 are each independently selected from hydrogen, an alkyl group, a haloalkyl group, an ester group, halogen, an aromatic group having 6-30 atoms in the ring thereof, or a heteroaromatic group having 5-30 atoms in the ring thereof; the ratio of m to n to p to q is (10-90):(10-90):(0.5-4):(0.05-1); and * represents a linking site. A photo-acid generator and a photo-base generator are both introduced into a main chain of the polymer and are uniformly distributed; and the polymer has a high optical transparency, and when a 248-nm-thick photoresist is prepared therefrom, a photolithographic pattern having a height-width ratio of 4:1 or higher and a relatively good line roughness can be obtained.

Description

Acrylate polymer and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of copolymers, and in particular to an acrylic acid ester polymer and a preparation method and application thereof. Background Art

[0002] The principle of chemically amplified photoresist was proposed as early as the 1980s. Subsequently, 248nm chemically amplified photoresist was developed. Due to its advantages in sensitivity and contrast, 248nm photolithography technology has become the most mainstream microlithography technology after g-line and i-line. The basic principle of chemically amplified photoresist is as follows: Acid-labile groups are suspended on the molecular chain of the polymer resin, and their presence makes the polymer insoluble in the developer. The photoacid generator (PAG) absorbs photon energy and generates H + , the H + During the subsequent baking process, it reacts with the acid-sensitive groups in the polymer resin to form leaving groups, causing the solubility of the polymer resin to change, thereby developing to obtain the desired structure.

[0003] At present, deep ultraviolet photoresists used in semiconductor processing all adopt chemical amplification systems. Traditional chemical amplification photoresists are compounded with photoacid generators and film-forming resins. In the post-baking stage, the photoacid generator generates H + Migration to the unexposed area makes it difficult to improve the resolution of the photoresist. At the same time, the system is particularly sensitive to the amine content in the environment, which reacts with the H generated by exposure. + A chemical reaction occurs, resulting in a loss of photoresist sensitivity in the exposed areas.

[0004] Summary of the Invention

[0005] Based on this, the present invention provides an acrylate polymer with high optical transparency, in which a photoacid generator and a photobase generator are simultaneously introduced into the polymer, and the uniform distribution of the photoacid generator and the photobase generator can be controlled.

[0006] The first aspect of the present invention provides an acrylic polymer comprising at least one repeating unit having a structure represented by formula (I):

[0007] wherein Ar1 and Ar2 each independently include an aromatic group having 6 to 30 ring atoms;

[0008] R1, R2, R3 and R4 are independently selected from hydrogen, alkyl, haloalkyl, ester, halogen, aromatic group with 6 to 30 ring atoms or heteroaromatic group with 5 to 30 ring atoms;

[0009] m, n, p and q are in the ratio of (10-90):(10-90):(0.5-4):(0.05-1), and * indicates a bonding site.

[0010] In one embodiment, Ar1 and Ar2 are each independently an aromatic group having 6 to 15 ring atoms.

[0011] In one embodiment, Ar1 and Ar2 are each independently selected from the group consisting of:

[0012] Each R5 is independently selected from a C1-C20 linear alkyl group, a C3-C20 cyclic alkyl group, a C1-C20 halogenated alkyl group, a C1-C20 ester group, or a halogen;

[0013] Each R6 is independently selected from a single bond or the group consisting of:

[0014] In one embodiment, R1, R2, R3 and R4 are each independently selected from hydrogen, a C1-C20 linear alkyl group, a C3-C20 cyclic alkyl group, a halogen, an aromatic group having 6 to 20 ring atoms, or a heteroaromatic group having 5 to 20 ring atoms.

[0015] In one embodiment, the acrylic polymer has a weight average molecular weight of 5,000 g / mol to 50,000 g / mol.

[0016] In one embodiment, the acrylic polymer has a photosensitive wavelength range of 190 nm to 290 nm.

[0017] In one embodiment, the acrylic polymer has a transmittance of greater than 95% under light having a wavelength of 300 nm to 450 nm.

[0018] A second aspect of the present application provides a method of preparing the acrylic polymer as described above, comprising the steps of:

[0019] mixing a hydroxyl group-containing aryl acrylate of formula (a), an isobornyl acrylate of formula (b), a double-bond-containing photo-acid generator of formula (c), a double-bond-containing photo-base generator of formula (d), and an initiator, and preparing the acrylic polymer as described above through a polymerization reaction;

[0020] In one embodiment, the hydroxyl group-containing aryl acrylate, the isobornyl acrylate, the double-bond-containing photo-acid generator, and the double-bond-containing photo-base generator are in the molar ratio of (10-90):(10-90):(0.5-4):(0.05-1).

[0021] In one embodiment, the temperature of the polymerization reaction is 60-90℃, and the time is 1-30h.

[0022] In one embodiment, a chain transfer agent is added in the preparation of the acrylic polymer to control the molecular weight and distribution width of the acrylic polymer.

[0023] The third aspect of the present application provides a photosensitive resin comprising the acrylic polymer as described above or prepared according to the preparation method as described above.

[0024] The fourth aspect of the present application provides a photoresist comprising the photosensitive resin as described above.

[0025] In one embodiment, the photoresist further comprises an additive and a solvent.

[0026] In one embodiment, the photoresist comprises the photosensitive resin 10-30%, the additive 0.5-2% and the solvent 68-89.5% by mass.

[0027] In one embodiment, the photoresist is a chemical amplification photoresist, and the exposure wavelength of the chemical amplification photoresist is 248nm.

[0028] The present application has at least the following beneficial effects:

[0029] The acrylic polymer represented by formula (I) provided by the present application can control the uniform distribution of the photoacid generator and the photoacid generator by simultaneously introducing the photoacid generator and the photoacid generator into the polymer. Among them, the N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide introduced is a photoacid generator, which can absorb 248nm photon energy to generate H + , and the photoacid generator can react with H + , reduce the diffusion range of the photoacid generator, and the introduction of the hydroxyl-substituted aryl acrylate and isopropyl acrylate can improve the adhesion and etching resistance of the photoresist.

[0030] In summary, the present application simultaneously introduces the photoacid generator and the photoacid generator into the polymer main chain, which can control the uniform distribution of the photoacid generator and the photoacid generator, the wavelength range of the photosensitive wavelength is 190-290nm, and the transmittance under the condition of wavelength of 300-450nm is greater than 95%, which shows that it has the characteristics of good transparency. The 248nm thick photoresist can obtain a high-width ratio of 4:1 or more (5:1 in some embodiments) and a good line roughness of the photoresist pattern.

[0031] In addition, the preparation method of the acrylate polymer is simple, safe and suitable for large-scale production. BRIEF DESCRIPTION OF DRAWINGS

[0032] Fig. 1 is an infrared spectrum of the acrylate polymer according to an embodiment of the present application;

[0033] Fig. 2 is a hydrogen nuclear magnetic resonance spectrum of the acrylate polymer according to an embodiment of the present application;

[0034] Fig. 3 is a transmittance of the acrylate polymer at different wavelengths according to an embodiment of the present application. DETAILED DESCRIPTION

[0035] The present application will be further described below in conjunction with the embodiments and examples. It should be understood that these examples are only used to illustrate the present application and not intended to limit the scope of the present application. Furthermore, it should be understood that those skilled in the art can make various modifications or changes to the present application after reading the content of the present application, and these equivalent forms also fall within the scope of the appended claims of the present application.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application.

[0037] Terminology

[0038] Unless otherwise defined, or if used in contradiction with the context, the terms or phrases used herein have the following meanings:

[0039] The selection range of the terms "and / or", "or / and", "and / or" used in the present application includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, which includes any two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", "and / or", it should be understood that the technical solution undoubtedly includes the technical solution connected by "logical and" in the present application, and also undoubtedly includes the technical solution connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C and D (i.e. the technical solution connected by "logical or"), and also includes any and all combinations of A, B, C and D, i.e. includes the combination of any two or any three of A, B, C and D, and also includes the four-item combination of A, B, C and D (i.e. the technical solution connected by "logical and").

[0040] In the present application, the meaning of "multiple" or "several" is at least two, such as two, three, etc., and the meaning of "multiple layers" or "several layers" is at least two layers, such as two layers, three layers, etc., unless otherwise explicitly and specifically limited. In the description of the present application, the meaning of "several" is at least one or more than one, such as one, two, etc., unless otherwise explicitly and specifically limited.

[0041] If not specifically stated, all steps of the present application can be performed in sequence or randomly. For example, the method includes steps (a) and (b), which means that the method can include steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method is mentioned to further include step (c), which means that step (c) can be added to the method in any order, for example, the method can include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0042] In the present application, "preferably", "more preferably", "even more preferably" and the like are only used to describe the embodiments or examples with better effects, and it should be understood that they do not constitute a limitation on the protection scope of the present application.

[0043] In the present application, "further", "even further", "in particular" and the like are used for description purposes, indicating differences in content, but should not be understood as a limitation on the protection scope of the present application.

[0044] In the present application, the terms "first", "second", "third", "fourth", "fifth" and the like in the "first aspect", "second aspect", "third aspect", "fourth aspect", "fifth aspect" and the like are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the technical features indicated. Moreover, "first", "second", "third", "fourth", "fifth" and the like only serve the purpose of non-exhaustive enumeration and description, and should be understood as not constituting a closed limitation on the quantity.

[0045] In the present application, in the technical features described in an open manner, both the closed technical solution consisting of the enumerated features and the open technical solution containing the enumerated features are included.

[0046] In the present application, with respect to the numerical interval (i.e. numerical range), if no special instructions are given, the optional numerical distribution within the above-mentioned numerical interval is considered to be continuous, and includes the two numerical end points (i.e. the minimum value and the maximum value) of the numerical range, as well as every numerical value between the two numerical end points. If no special instructions are given, when the numerical interval only points to the integers within the numerical interval, the two end point integers of the numerical range and every integer between the two end points are included. In addition, when multiple ranges are provided to describe a feature or a characteristic, these ranges can be combined. In other words, unless otherwise indicated, the ranges disclosed herein should be understood to include any and all sub-ranges therein.

[0047] In the present application, the number of atoms described by a numerical range includes the two integer end points of the numerical range, as well as every integer in the two end points. For example, "C1-C10 alkyl" represents an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0048] In the present application, When R is selected from a single bond, represents represents the connection site of the non-limiting substituent R to the benzene ring.

[0049] In the present application, "*" represents the connection site.

[0050] In the present application, "halogen" or "halo" refers to -F, -Cl, -Br or -I.

[0051] In the present application, the term "alkyl" refers to a saturated hydrocarbon radical of a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof, which loses one hydrogen atom to form a monovalent radical. Phrases containing this term, for example, "Ci-Cio alkyl" means an alkyl group containing from 1 to 10 carbon atoms, each occurrence of which can be independently Ci alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, or Cio alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1 -propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1 -butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-l -propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-l -butyl (-CH2CH2CH(CH3)2), 2-methyl-l -butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3, and octyl (-(CH2)7CH3).

[0052] In the present application, "haloalkyl" refers to an alkyl group substituted with one or more halogen (chlorine, fluorine, bromine or iodine) atoms. Polyhaloalkyl groups have the same or mixed types of halogen atoms. "Perhaloalkyl" refers to an alkyl group in which each hydrogen atom is replaced by a halogen atom. A haloalkyl group in which a particular carbon atom is "perhalo" refers to the replacement of all hydrogen atoms attached to that carbon with halogen atoms. Representative mono-, di-, and trihaloalkyl groups include chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1,1-dichloromethyl, 1,1-dibromomethyl, 1,1-dichloropropyl, 1,2-dibromopropyl, 2,3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3-bromopropyl, trifluoromethyl, trichloromethyl, and the like.

[0053] In the present application, "cycloalkyl" refers to a non-aromatic hydrocarbon containing ring carbon atoms, which can be a monocycloalkyl group, or a spirocycloalkyl group, or a bridged cycloalkyl group. Phrases containing this term, such as "C3-C10 cycloalkyl", refer to a cycloalkyl group containing 3 to 10 carbon atoms, each occurrence of which can independently be a C3 cycloalkyl group, a C4 cycloalkyl group, a C5 cycloalkyl group, a C6 cycloalkyl group, a C7 cycloalkyl group, a C8 cycloalkyl group, a C9 cycloalkyl group, or a C10 cycloalkyl group. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Additionally, "cycloalkyl" can also contain one or more double bonds, representative examples of cycloalkyl groups containing double bonds include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutadienyl.

[0054] In the present application, "ester" is a functional group of an ester in a carboxylic acid derivative, the structural formula of which is -COOR (R is generally an alkyl group or other non-H group), and the ester group mainly undergoes a hydrolysis reaction.

[0055] In the present application, "ring atom number" indicates the number of atoms among the atoms constituting a ring itself of a structural compound obtained by bonding atoms into a ring shape (e.g., monocyclic compound, fused ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound). When the ring is substituted with a substituent, the atoms included in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below, unless otherwise specified. For example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, and the ring atom number of biphenyl is 12.

[0056] In the present application, the term "aryl, aryl group, or aromatic group" refers to a hydrocarbon group containing at least one aromatic ring, such as benzene, naphthalene, anthracene, fluoranthene, phenanthrene, chrysene, pyrene, benzopyrene, acenaphthene, fluorene, biphenyl, terphenyl, and derivatives of the above aryl groups.

[0057] In the present application, "halogen" is selected from fluorine, chlorine, bromine, iodine, or astatine.

[0058] In the present application, the term "arylene" refers to an aromatic hydrocarbon group derived by removing two hydrogen atoms from an aromatic ring compound, which can be a monocyclic arylene group, or a fused ring arylene group, or a polycyclic arylene group, and for the polycyclic ring species, at least one is an aromatic ring system. For example, "C6-C10 arylene" refers to an arylene group comprising 6 to 10 carbon atoms, which can be independently at each occurrence C6 arylene, C7 arylene, C8 arylene, C9 arylene or C10 arylene. Suitable examples include, but are not limited to: phenylene, biphenylene, naphthylene, anthracylene, phenanthrylene, rylenes, triphenylenes and derivatives thereof.

[0059] In the present application, the term "cycloalkylene" refers to a hydrocarbon group derived by removing two hydrogen atoms from a cycloalkyl group, which can be a monocyclic cycloalkylene group, or a spirocyclic cycloalkylene group, or a bridged cycloalkylene group, having two monovalent radical centers. For example, "C3-C10 cycloalkylene" refers to a cycloalkylene group comprising 3 to 9 carbon atoms, which can be independently at each occurrence C3 cycloalkylene, C4 cycloalkylene, C5 cycloalkylene, C6 cycloalkylene, C7 cycloalkylene, C8 cycloalkylene or C9 cycloalkylene. Suitable examples include, but are not limited to: cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene and cycloheptylene. In addition, the "cycloalkylene" can also contain one or more double bonds, and representative examples of cycloalkylene groups containing double bonds include cyclopentenylene, cyclohexenylene, cyclohexadienylene and cyclobutadienylene.

[0060] "Heteroaryl or heteroaromatic group or heteroaromatic radical" refers to an aromatic group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to a substituted or unsubstituted heteroaryl group comprising 5 to 40 ring atoms, preferably a heteroaryl group having 6 to 30 ring atoms, more preferably a heteroaryl group having 6 to 18 ring atoms, and particularly preferably a heteroaryl group having 6 to 14 ring atoms, and the heteroaryl group is optionally further substituted, and suitable examples include, but are not limited to: triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, perylene, quinoxaline, phenanthridine, berberine, quinazoline, quinazolinone, dibenzothiophene, dibenzofuran, carbazole and derivatives thereof.

[0061] The temperature parameters in the present application, unless otherwise specified, allow both constant temperature treatment and fluctuations within a certain temperature range. It should be understood that the constant temperature treatment allows fluctuations within the accuracy range controlled by the instrument. Fluctuations within a range such as ±5°C, ±4°C, ±3°C, ±2°C, ±1°C are allowed.

[0062] A detailed description of the present application is as follows:

[0063] The present application provides an acrylate polymer with high optical transparency, which simultaneously introduces a photoacid generator and a photobase generator into the polymer, and can control the uniform distribution of the photoacid generator and the photobase generator.

[0064] The first aspect of the present application provides an acrylate polymer, which comprises at least one repeating unit having a structure shown in formula (I):

[0065] wherein Ar1 and Ar2 independently comprise an aromatic group having 6 to 30 ring atoms;

[0066] R1, R2, R3 and R4 are independently selected from hydrogen, an alkyl group, a halogenated alkyl group, an ester group, a halogen, an aromatic group having 6 to 30 ring atoms, or a heteroaromatic group having 5 to 30 ring atoms;

[0067] The ratio of m, n, p and q is (10-90):(10-90):(0.5-4):(0.05-1), and * represents a connection site.

[0068] It can be understood that m includes but is not limited to 10, 20, 30, 40, 50, 60, 70, 80 or 90.

[0069] It can be understood that n includes but is not limited to 10, 20, 30, 40, 50, 60, 70, 80 or 90.

[0070] It can be understood that p includes but is not limited to 0.5, 1, 2, 3 or 4.

[0071] It can be understood that q includes but is not limited to 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.8 or 1.

[0072] In one embodiment, Ar1 and Ar2 independently comprise an aromatic group having 6 to 20 ring atoms, and Ar1 and Ar2 independently comprise a phenyl group, a naphthyl group and a biphenyl group without limitation.

[0073] In one embodiment, Ar1 and Ar2 are independently selected from the following groups:

[0074] Each R5 is independently selected from a C1-C20 chain alkyl group, a C3-C20 cyclic alkyl group, a C1-C20 halogenated alkyl group, a C1-C20 ester group or a halogen;

[0075] R6 is independently selected from a single bond or the following groups:

[0076] Further, each R5is independently selected from a C1-C20 linear alkyl group, a C3-C20 branched alkyl group, a C3-C20 cyclic alkyl group, a C1-C20 haloalkyl group, a C1-C20 ester group, or a halogen. Further, each R5is independently selected from a C1-C10 linear alkyl group, a C3-C10 branched alkyl group, a C3-C10 cyclic alkyl group, a C1-C10 fluoroalkyl group, a C2-C10 ester group, fluorine, chlorine, bromine, or iodine. Without limitation, each R5is independently a methyl group (-CH3), an ethyl group, a 1 -propyl group, a 2-propyl group, a 1 -butyl group, a 2-methyl- 1 -propyl group, a 2-butyl group, a 2-methyl-2-propyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-2-butyl group, a 3-methyl-2-butyl group, a 3-methyl- 1 -butyl group, a 2-methyl- 1 -butyl group, a 1 -hexyl group, a 2-hexyl group, a 3-hexyl group, a 2-methyl-2-pentyl group, a 3-methyl-2-pentyl group, a 4-methyl-2-pentyl group, a 3-methyl-3-pentyl group, a 2-methyl-3-pentyl group, a 2,3-dimethyl-2-butyl group, a 3,3-dimethyl-2-butyl group, a n-octyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a trifluoromethyl group (-CF3), or a fluorine group (-F). Further, each R5is independently selected from -F, -CH3, or -CF3.

[0077] In one embodiment, each of R1, R2, R3, and R4is independently selected from hydrogen, a C1-C20 chain alkyl group, a C3-C20 cyclic alkyl group, a halogen, an aromatic group having 6 to 20 ring atoms, or a heteroaromatic group having 5 to 20 ring atoms. Further, each of R1, R2, R3, and R4is independently selected from hydrogen, a C1-C10 chain alkyl group, a C3-C10 cyclic alkyl group, fluorine, chlorine, bromine, iodine, an aromatic group having 6 to 15 ring atoms, or a heteroaromatic group having 5 to 15 ring atoms. Without limitation, each of R1, R2, R3, and R4is independently a methyl group (-CH3), an ethyl group, a 1 -propyl group, a 2-propyl group, a 1 -butyl group, a 2-methyl- 1 -propyl group, a 2-butyl group, a 2-methyl-2-propyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-2-butyl group, a 3-methyl-2-butyl group, a 3-methyl- 1 -butyl group, a 2-methyl- 1 -butyl group, a 1 -hexyl group, a 2-hexyl group, a 3-hexyl group, a 2-methyl-2-pentyl group, a 3-methyl-2-pentyl group, a 4-methyl-2-pentyl group, a 3-methyl-3-pentyl group, a 2-methyl-3-pentyl group, a 2,3-dimethyl-2-butyl group, a 3,3-dimethyl-2-butyl group, a n-octyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a trifluoromethyl group (-CF3), or a fluorine group (-F). Further, each R5is independently selected from -F, -CH3, or -CF3.

[0078] In one embodiment, the acrylate-based polymer is a white solid. Further, the weight average molecular weight of the acrylate-based polymer is 5000 g / mol to 50000 g / mol, including but not limited to 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, 10000 g / mol, 12000 g / mol, 15000 g / mol, 18000 g / mol, 20000 g / mol, 25000 g / mol, 30000 g / mol, 35000 g / mol, 40000 g / mol, 45000 g / mol or 50000 g / mol. Preferably, the weight average molecular weight of the acrylate-based polymer is 6000 g / mol to 10000 g / mol. Further preferably, the weight average molecular weight of the acrylate-based polymer is 7000 g / mol to 9000 g / mol.

[0079] In one embodiment, the acrylate-based polymer has a photosensitive wavelength range of 190 nm to 290 nm.

[0080] In one embodiment, the acrylate-based polymer has a transmittance of greater than 95% under light having a wavelength of 300 nm to 450 nm.

[0081] A second aspect of the present application provides a method for preparing the acrylate-based polymer as described above, comprising the following steps:

[0082] mixing a hydroxyl group-containing aryl acrylate represented by formula (a), isobornyl acrylate represented by formula (b), a double-bond-containing photo-acid generator represented by formula (c), a double-bond-containing photo-base generator represented by formula (d) and an initiator to prepare the acrylate-based polymer as described above through a polymerization reaction;

[0083] In one embodiment, the molar ratio of the hydroxyl group-containing aryl acrylate, the isobornyl acrylate, the double-bond-containing photo-acid generator, the double-bond-containing photo-base generator is (10-90):(10-90):(0.5-4):(0.05-1).

[0084] In one embodiment, the polymerization reaction is carried out at a temperature of 60°C to 90°C for a time period of 1 h to 30 h.

[0085] It is understood that a chain transfer agent can be optionally added during the preparation of the polymer to control the molecular weight and the distribution width of the acrylate-based polymer. Further, the present application does not particularly limit the type of the chain transfer agent, and any conventional type can be used, including but not limited to isooctyl 3-mercaptopropionate (IOMP), which is commercially available.

[0086] In one embodiment, the method for preparing the acrylate polymer as described above comprises the following steps:

[0087] The hydroxyl group-containing aryl acrylate represented by formula (a), the isobornyl acrylate represented by formula (b), the double-bond-containing photo-acid generator represented by formula (c), the double-bond-containing photo-base generator represented by formula (d), the chain transfer agent and the initiator are mixed to prepare the acrylate polymer as described above through a polymerization reaction.

[0088] In one embodiment, the double-bond-containing photo-acid generator is N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, and has the following structural formula: CAS: 133710-62-0.

[0089] In one embodiment, the double-bond-containing photo-base generator is acetophenone oxime acrylate, and has the following structural formula: It is prepared according to the following route:

[0090] The acetophenone oxime acrylate is prepared by mixing and reacting the acetophenone oxime and the acryloyl chloride.

[0091] In one embodiment, the molar ratio of the acetophenone oxime and the acryloyl chloride is 1: (1-3). In the following specific example, it is 1:1.

[0092] In one embodiment, the reaction temperature of the acetophenone oxime and the acryloyl chloride is 0-20°C, and the reaction time is 0.5-5h. In the following specific example, the temperature is 0°C, and the time is 2h.

[0093] In one embodiment, the double-bond-containing photo-base generator is acetophenone oxime methacrylate, and has the following structural formula: It is prepared according to the following route:

[0094] The acetophenone oxime methacrylate is prepared by mixing and reacting the acetophenone oxime and the methacryloyl chloride.

[0095] In one embodiment, the molar ratio of the acetophenone oxime and the methacryloyl chloride is 1: (1-3). In the following specific example, it is 1:1.

[0096] In one embodiment, the reaction temperature of the acetophenone oxime and the methacryloyl chloride is 0-20°C, and the reaction time is 0.5-5h. In the following specific example, the temperature is 0°C, and the time is 2h.

[0097] The third aspect of the present application provides a photosensitive resin comprising the acrylate polymer as described above or prepared according to the method as described above.

[0098] The fourth aspect of the present application provides a photoresist, comprising the photosensitive resin as described above.

[0099] In one embodiment, the photoresist further comprises an additive and a solvent.

[0100] In one embodiment, the photoresist comprises the photosensitive resin as described above 10% to 30% by mass, the additive 0.5% to 2% by mass, and the solvent 68% to 89.5% by mass.

[0101] It is understood that in the present application, the photoresist comprises the photosensitive resin as described above 10% to 30% by mass, including but not limited to 10%, 15%, 20%, 25%, or 30%.

[0102] It is understood that in the present application, the photoresist comprises the additive 0.5% to 2% by mass, including but not limited to 0.5%, 1%, 1.5%, or 2%.

[0103] It is understood that the additive of the present application is a conventional additive in the field of photoresist, which can be selected from one or more of leveling agents, dispersants, defoaming agents, and other types of additives, and the present application does not have special requirements for the specific type of additive, which can be a conventional type in the field of photoresist. In one specific example, the additive is a leveling agent, which is further KL-406 leveling agent.

[0104] It is understood that in the present application, the photoresist comprises the solvent 68% to 89.5% by mass, including but not limited to 68%, 70%, 75%, 79%, 80%, 85%, or 89.5%.

[0105] It is understood that the solvent of the present application is a conventional solvent in the field of photoresist, and the present application does not have special requirements for the specific type of solvent. In one specific example, the solvent is propylene glycol methyl ether acetate.

[0106] In one embodiment, the photoresist is a chemically amplified photoresist. Further, the exposure wavelength of the chemically amplified photoresist is 248 nm. Still further, the chemically amplified photoresist is a thick photoresist.

[0107] In one embodiment, the thickness of the thick photoresist is 2 μm to 200 μm.

[0108] The following are specific examples.

[0109] The raw materials and reagents involved in the following specific examples can be obtained commercially or prepared by those skilled in the art according to known methods.

[0110] The testing method of the present invention is as follows:

[0111] 1. Ontology representation:

[0112] (1) Optical transmittance: UV spectrophotometer.

[0113] (2) Glass transition temperature (T g ):DSC.

[0114] (3) Weight average molecular weight: GPC test.

[0115] 2. Testing of product performance after application:

[0116] Film thickness test: film thickness meter.

[0117] Resolution: Microscope.

[0118] Exposure sensitivity evaluation: photolithography machine.

[0119] Height:Aspect ratio:SEM.

[0120] Example 1

[0121] 8.9 g of 4-hydroxyphenyl methacrylate (CAS: 31480-93-0), 98.9 g of isobornyl methacrylate (CAS: 7534-94-3), 0.8 g of N-(trifluoromethanesulfonyloxy)-5-norbornene-2,3-dicarboxamide, a photoacid generator with a double bond 0.5g of acetophenone oxime acrylate, a photogenerator with a double bond A mixture of 0.5 g of the chain transfer agent isooctyl mercaptopropionate (IOMP) and 2 g of azobisisobutyronitrile (AIBN) was added to a flask containing 110 g of diethylene glycol dimethyl ether. After the addition was complete, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photoacid generator and a photobase generator. The reaction solution was then added dropwise to n-heptane to obtain a precipitate, which was filtered and air-dried to obtain the photosensitive polyacrylic resin P1. The weight average molecular weight M of the film-forming resin was measured by GPC. w The molecular weight distribution PDI is 4.11.

[0122] Example 2

[0123] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.8 g of a double-bonded photo-acid generator N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.5 g of a double-bonded photo-base generator phenylethanone oxime acrylate, 1 g of a chain transfer agent IOMP, etc., and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition was completed, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photo-acid generator and a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P2. The weight average molecular weight Mw of the film-forming resin was 19858 g / mol, and the molecular weight distribution PDI was 11.4. w Example 3

[0124] Example 3

[0125] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.8 g of a double-bonded photo-acid generator N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.5 g of a double-bonded photo-base generator phenylethanone oxime acrylate, 4 g of a chain transfer agent IOMP, etc., and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition was completed, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photo-acid generator and a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P3. The weight average molecular weight Mw of the film-forming resin was 7974 g / mol, and the molecular weight distribution PDI was 2.2. w Example 3

[0126] The photosensitive polyacrylic resin P3 was characterized by infrared spectroscopy, and the results are shown in FIG. 1. As shown in FIG. 1, 2971 cm -1 , 2886 cm -1 , 1720 cm -1 , and 1490 cm -1The characteristic absorption peak of the nearby benzene ring. The results of the hydrogen nuclear magnetic resonance spectrum of the resin P3 are shown in Figure 2. It can be seen from Figure 2 that b and c are the characteristic peaks of the photoacid generator, and a is the characteristic peak of the photo base generator, indicating that the photoacid generator and the photobase generator are successfully polymerized on the resin. The transmittance of the resin P3 at different wavelengths is tested, and the results are shown in Figure 3. It can be seen from Figure 3 that the photosensitive wavelength range of the polymer is 190 nm to 290 nm, and the transmittance under the light condition of 300 nm to 450 nm is greater than 95%, indicating that the optical transparency is high.

[0127] Example 4

[0128] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 67.2 g of isobornyl methacrylate (CAS: 5888-33-5), 0.8 g of a double-bond-containing photoacid generator N- (trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.5 g of a double-bond-containing photobase generator phenylethanone oxime acrylate, 4 g of a chain transfer agent IOMP, etc., and 1 g of azobisisobutyronitrile (AIBN) is added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition is complete, the reaction mixture is stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic acid resin solution containing both a photoacid generator and a photobase generator. Then the reaction solution is added dropwise into n-heptane to obtain a precipitate, which is filtered, air-dried, and the product is a photosensitive polyacrylic acid resin P4. The weight average molecular weight M w of the film-forming resin is 7533 g / mol, and the molecular weight distribution PDI is 2.24.

[0129] Example 5

[0130] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.8 g of a double-bond-containing photoacid generator N- (trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.54 g of a double-bond-containing photobase generator phenylethanone oxime methacrylate 4 g of a chain transfer agent IOMP, etc., and 1 g of azobisisobutyronitrile (AIBN) is added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition is complete, the reaction mixture is stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic acid resin solution containing both a photoacid generator and a photobase generator. Then the reaction solution is added dropwise into n-heptane to obtain a precipitate, which is filtered, air-dried, and the product is a photosensitive polyacrylic acid resin P5. The weight average molecular weight M w of the film-forming resin is 7755 g / mol, and the molecular weight distribution PDI is 3.57.

[0131] Example 6

[0132] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 67.2 g of isobornyl acrylate, 0.8 g of a double-bond-containing photo-acid generator N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.54 g of a double-bond-containing photo-base generator phenylethanone oxime methacrylate, 4 g of a chain transfer agent IOMP, and the like, and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition was completed, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photo-acid generator and a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P6. The weight average molecular weight Mw of the film-forming resin was 10,000 g / mol, and the molecular weight distribution PDI was 3.17, as measured by GPC. w was 10,000 g / mol, and the molecular weight distribution PDI was 3.17.

[0133] Example 7

[0134] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 67.2 g of isobornyl acrylate, 0.8 g of a double-bond-containing photo-acid generator N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.54 g of a double-bond-containing photo-base generator phenylethanone oxime methacrylate, 4 g of a chain transfer agent IOMP, and the like, and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition was completed, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photo-acid generator and a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P6. The weight average molecular weight Mw of the film-forming resin was 10,000 g / mol, and the molecular weight distribution PDI was 3.17, as measured by GPC. w was 10,000 g / mol, and the molecular weight distribution PDI was 3.17.

[0135] Example 8

[0136] This example did not add a chain transfer agent, and was as follows:

[0137] A mixture of 8.9 g of 4-hydroxyphenyl methacrylate, 98.9 g of isobornyl methacrylate, 0.8 g of a double-bond-containing photo-acid generator N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 0.5 g of a double-bond-containing photo-base generator phenylethanone oxime acrylate, and 2 g of azobisisobutyronitrile (AIBN) was added to a flask containing 110 g of diethylene glycol dimethyl ether. After the addition was complete, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photo-acid generator and a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P11. The weight average molecular weight Mw of the film-forming resin was 42916 g / mol, and the molecular weight distribution PDI was 3.66. w The weight average molecular weight Mw of the film-forming resin was 42916 g / mol, and the molecular weight distribution PDI was 3.66.

[0138] Comparative Example 1

[0139] This comparative example did not include a photo-acid generator, and was as follows:

[0140] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.5 g of a double-bond-containing photo-base generator phenylethanone oxime acrylate, 2 g of a chain transfer agent IOMP, and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 105 g of diethylene glycol dimethyl ether. After the addition was complete, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing a photo-base generator but not a photo-acid generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P8. The weight average molecular weight Mw of the film-forming resin was 13593 g / mol, and the molecular weight distribution PDI was 4.58. w The weight average molecular weight Mw of the film-forming resin was 42916 g / mol, and the molecular weight distribution PDI was 3.66.

[0141] Comparative Example 2

[0142] This comparative example did not include a photo-base generator, and was as follows:

[0143] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.8 g of a double-bond-containing photo-acid generator N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxamide, 4 g of a chain transfer agent IOMP, and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition was complete, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing a photo-acid generator but not a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was a photosensitive polyacrylic resin P9. The weight average molecular weight Mw of the film-forming resin was 42916 g / mol, and the molecular weight distribution PDI was 3.66.w The molecular weight distribution PDI is 7900 g / mol and 2.4.

[0144] Comparative Example 3

[0145] This comparative example does not contain a photoacid generator and a photobase generator, and the details are as follows:

[0146] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 2 g of chain transfer agent IOMP, etc. and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 105 g of diethylene glycol dimethyl ether. After the addition was completed, the reaction mixture was stirred at 78 ° C for 8 hours to obtain a photosensitive polyacrylic resin solution that did not contain a photobase generator and a photoacid generator. The reaction solution was then added dropwise to n-heptane to obtain a precipitate, which was filtered and dried with air blast. The product was the photosensitive polyacrylic resin P10. The weight average molecular weight M of the film-forming resin was measured by GPC. w The molecular weight distribution PDI is 8085 g / mol and 2.2.

[0147] Comparative Example 4

[0148] In this comparative example, the photoacid generator is replaced with triphenylsulfonium 2,3,5,6-tetrafluoro-4-(methacryloyloxy)benzenesulfonate, as follows:

[0149] 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.8 g of triphenylsulfonium 2,3,5,6-tetrafluoro-4-(methacryloyloxy)benzenesulfonate (a photoacid generator with a double bond) (CAS: 915090-37-8), 0.5g of a photobase generator with a double bond, acetophenone oxime acrylate, 4g of a chain transfer agent IOMP, and 1g of azobisisobutyronitrile (AIBN) were added to a flask containing 102g of diethylene glycol dimethyl ether. After the addition was completed, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing both a photoacid generator and a photobase generator. The reaction solution was then added dropwise to n-heptane to obtain a precipitate, which was filtered and dried with air blast. The product was the photosensitive polyacrylic resin P12. The weight average molecular weight M of the film-forming resin was measured by GPC. w The molecular weight distribution PDI is 3.44.

[0150] Comparative Example 5

[0151] In this comparative example, the photoacid generator is replaced with N-hydroxy-5-norbornene-2,3-dicarboximide perfluorobutyl sulfonate, as follows:

[0152] A mixture of 26.7 g of 4-hydroxyphenyl methacrylate, 71.7 g of isobornyl methacrylate, 0.8 g of a double-bonded photo-acid generator N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide perfluorobutyl sulfonate (CAS: 307531-76-6), 0.5 g of a double-bonded photo-base generator phenylacetone oxime acrylate, 4 g of a chain transfer agent IOMP, etc., and 1 g of azobisisobutyronitrile (AIBN) was added to a flask containing 102 g of diethylene glycol dimethyl ether. After the addition was complete, the reaction mixture was stirred at 78°C for 8 hours to obtain a photosensitive polyacrylic resin solution containing a photo-acid generator and a photo-base generator. The reaction solution was then added dropwise into n-heptane to obtain a precipitate, which was filtered, air-dried, and the product was the photosensitive polyacrylic resin P13. The weight average molecular weight Mw of the film-forming resin was 8850 g / mol, and the molecular weight distribution PDI was 3.52. w The weight average molecular weight Mw of the film-forming resin was 8850 g / mol, and the molecular weight distribution PDI was 3.52.

[0153] Application Example 1

[0154] Application of the resin of Example 3 in a positive photoresist:

[0155] A photoresist was prepared by mixing the film-forming resin 20%, the solvent propylene glycol methyl ether acetate 79%, and the additive 1% by mass, dissolving them thoroughly, and filtering through a 0.22-μm filter, and a photolithography experiment was then performed. The process was: coating - pre-baking - exposure - development - microscope observation - stripping.

[0156] Application Example 2

[0157] Application of the resin of Example 4 in a positive photoresist:

[0158] A photoresist was prepared by mixing the film-forming resin 20%, the solvent propylene glycol methyl ether acetate 79%, and the additive 1% by mass, dissolving them thoroughly, and filtering through a 0.22-μm filter, and a photolithography experiment was then performed. The process was: coating - pre-baking - exposure - development - microscope observation - stripping.

[0159] Application Comparative Example 1

[0160] Application of the resin of Comparative Example 2 in a positive photoresist:

[0161] A photoresist was prepared by mixing the film-forming resin 20%, the solvent propylene glycol methyl ether acetate 79%, and the additive 1% by mass, dissolving them thoroughly, and filtering through a 0.22-μm filter, and a photolithography experiment was then performed. The process was: coating - pre-baking - exposure - development - microscope observation - stripping.

[0162] Application Comparative Example 2

[0163] Application of the resin of Comparative Example 3 in a positive photoresist:

[0164] The film forming resin 20%, solvent propylene glycol methyl ether acetate 79% and additives 1% were mixed in the following mass percentages, dissolved thoroughly, filtered through a 0.22 micron filter membrane to prepare a photoresist, and then a photolithography experiment was performed. Process: coating - pre-baking - exposure - development - microscope observation - stripping.

[0165] Test:

[0166] 1. The performance characterization results of the acrylate polymers of the examples and comparative examples are shown in Table 1 below.

[0167] Table 1

[0168] As can be seen from Table 1, the resins M w of Examples 3, 4, Comparative Example 2 and Comparative Example 3 have a molecular weight of 7500 g / mol to 8500 g / mol and a small molecular weight distribution PDI (less than 2.5), and preferably the tests of the products after the application of the polymers in photoresists are carried out.

[0169] 2. The test results of the photoresists after exposure and development using a photolithography machine are shown in Table 2 below.

[0170] Table 2

[0171] As can be seen from Table 2, both Examples 1 and 2 can obtain photoresist patterns with high resolution, high exposure sensitivity, high aspect ratio of more than 4:1 and good line roughness, and in particular, Example 1 can obtain photoresist patterns with high resolution, high exposure sensitivity, high aspect ratio of more than 5:1 and good line roughness.

[0172] The technical features of the above-described examples can be combined in any manner. In order to make the description concise, not all possible combinations of the technical features in the above-described examples are described, however, as long as the combinations of the technical features do not contradict each other, they should be considered as within the scope of the present disclosure.

[0173] The above-mentioned embodiments only express several implementation manners of the present application, facilitate concrete and detailed understanding of the technical solutions of the present application, but cannot be understood as a limitation on the patent protection scope of the present application. It should be noted that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. It should be understood that, on the basis of the technical solutions provided by the present application, the technical solutions obtained by logical analysis, reasoning or limited experiments by the skilled person in the art all belong to the protection scope of the appended claims of the present application. Therefore, the protection scope of the present application patent should be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. An acrylic acid ester polymer, characterized in that It comprises at least one repeating unit having a structure shown in formula (I): wherein Ar1 and Ar2 each independently include an aromatic group having 6 to 30 ring atoms; R1, R2, R3 and R4 are independently selected from hydrogen, alkyl, haloalkyl, ester, halogen, aromatic group with 6 to 30 ring atoms or heteroaromatic group with 5 to 30 ring atoms; The ratios of m, n, p, and q are (10-90):(10-90):(0.5-4):(0.05-1), and * indicates the linking site.

2. The acrylic polymer according to claim 1, wherein The Ar1 and Ar2 are independently selected from the following groups: Each R5 is independently selected from a C1-C20 chain alkyl group, a C3-C20 cycloalkyl group, a C1-C20 haloalkyl group, a C1-C20 ester group or a halogen group; R6 are each independently selected from a single bond or a group as shown below:

3. The acrylic polymer according to claim 1, wherein R1, R2, R3 and R4 are independently selected from hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, halogen, aromatic group with 6 to 20 ring atoms or heteroaromatic group with 5 to 20 ring atoms.

4. The acrylic polymer according to any one of claims 1 to 3, characterized in that Satisfy at least one of the following (1) to (3): (1) The weight average molecular weight of the acrylic polymer is 5000 g / mol to 50000 g / mol; (2) The photosensitivity wavelength range of the acrylic polymer is 190 nm to 290 nm; (3) The transmittance of the acrylic polymer under light conditions with a wavelength of 300 nm to 450 nm is greater than 95%.

5. A method for preparing an acrylic acid ester polymer according to any one of claims 1 to 4, characterized in that: The steps include: The acrylate polymer according to any one of claims 1 to 4 is prepared by mixing a hydroxyl aromatic acrylate represented by formula (a), an isobornyl acrylate represented by formula (b), a photoacid generator with a double bond represented by formula (c), a photobase generator with a double bond represented by formula (d), and an initiator, and performing a polymerization reaction; 6. The method for preparing an acrylic acid ester polymer according to claim 5, wherein: Satisfy at least one of the following (1) to (2): (1) The molar ratio of the hydroxyaryl acrylate, isobornyl acrylate, photoacid generator with double bonds, and photobase generator with double bonds is (10-90):(10-90):(0.5-4):(0.05-1); (2) The polymerization temperature is 60°C to 90°C, and the polymerization time is 1h to 30h.

7. A photosensitive resin, characterized in that: The invention comprises the acrylic acid ester polymer according to any one of claims 1 to 4 or the acrylic acid ester polymer prepared according to the preparation method according to any one of claims 5 to 6.

8. A photoresist, characterized in that The invention comprises the photosensitive resin according to claim 7.

9. The photoresist according to claim 8, characterized in that The photoresist further comprises additives and solvents; Calculated by mass percentage, the photosensitive resin according to claim 7 comprises 10% to 30%, additives 0.5% to 2% and solvents 68% to 89.5%.

10. The photoresist according to any one of claims 8 to 9, characterized in that The photoresist is a chemically amplified photoresist, and the exposure wavelength of the chemically amplified photoresist is 248 nm.

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