Sulfonate-based photoacid generator, its manufacturing method, patterning method, resist composition, and use thereof

Abstract

The present invention provides a sulfonate-based photoacid generator, a method for producing the same, a patterning method, a resist composition, and uses thereof. The sulfonate-based photoacid generator has the general formula (I), where R 1 is a substituted or unsubstituted C2 to C 25 Hydrocarbon groups, substituted or unsubstituted C2-C 25 Alkoxy groups, substituted or unsubstituted C2-C 25 In particular, -CH2- may be replaced by -O-, -S-, -CO-, -O-CO- or -COO-, and in particular, a C atom may be replaced by an N atom, and R 1 At the end of the 10 containing an epoxy group of R 2 is C1~C 20 Alkyl groups of C6 to C 18 The sulfonate-based photoacid generator is any one selected from the group consisting of a substituted or unsubstituted aryl group, a camphoryl group, a camphorquinone group, and an azidonaphthalenone group. The sulfonate-based photoacid generator can reduce the diffusion of photoacid molecules and improve the robustness of lithography patterns.

Description

[Technical Field]

[0001] This application is based on and claims priority from a Chinese application bearing CN Application No. 202211038021.3 and filed on August 26, 2022, the disclosure of which is hereby incorporated in its entirety into this application.

[0002] The present invention relates to the technical field of photosensitive materials, and more particularly to a sulfonate-based photoacid generator and its preparation method, patterning method, resist composition and use thereof. [Background technology]

[0003] Photoacid generators are a key component of chemically amplified photoresists, and their structure and performance have a significant impact on lithographic images. With the development of the semiconductor industry, the demand for higher-resolution patterns is increasing, along with a broader range of photoacid generators available and increasing demands for their performance, particularly for properties such as low diffusibility, high solubility, and high acid generation rate. Naphthalic anhydride sulfonate compounds are known to be used as photogenerators in the semiconductor field, but most conventional resist compositions require the addition of auxiliary agents to suppress acid migration or improve pattern robustness. Summary of the Invention

[0004] The main object of the present invention is to provide a sulfonate-based photoacid generator, a method for producing the same, a patterning method, a resist composition, and use thereof, in order to solve the problems of acid migration and poor fastness of lithography patterns present in the prior art.

[0005] In order to achieve the above object, according to one aspect of the present invention, there is provided a sulfonate-based photoacid generator having the following general formula (I): [ka] [In the formula, R 1 is a substituted or unsubstituted C2 to C 25Hydrocarbon groups, substituted or unsubstituted C2-C 25 Alkoxy groups, substituted or unsubstituted C2-C 25 In particular, -CH2- may be substituted by -O-, -S-, -CO-, -O-CO- or -COO-, and in particular, a C atom may be substituted by an N atom, and a substituted or unsubstituted C2 to C6 alkylthio group is 25 Hydrocarbon groups, substituted or unsubstituted C2-C 25 Alkoxy groups, substituted or unsubstituted C2-C 25 At least one substituted or unsubstituted C2-C alkylthio group at the end of the alkylthio group 10 containing an epoxy group of R 2 is C1~C 20 Alkyl groups of C6 to C 18 is any one selected from the group consisting of a substituted or unsubstituted aryl group of the formula (I), a camphoryl group, a camphorquinone group, and an azidonaphthalenone group.]

[0006] According to another aspect of the present invention, there is provided a method for preparing the aforementioned sulfonate-based photoacid generator, the method comprising: 1 ' a step S1 of reacting compound 2 with Y to form compound 2; a step S2 of reacting compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to form a hydroxylamine compound; and a step S3 of reacting the hydroxylamine compound with R 2 SO2X 2 or (R 2 and step S3 of esterifying the compound with SO2)2O to obtain a sulfonate-based photoacid generator. The structural formulae of Compound 1 and Compound 2 are as follows: [ka] [In the formula, X 1 represents any one selected from the group consisting of -H, -OH, -SH, and a halogen atom; Y represents any one selected from the group consisting of -OH, -CH=CH2, -C≡CH, and a halogen atom; X 2 is a halogen atom, and R 1'Y is X in compound 1 1 React with the substituent R 1 When Y is a halogen atom, R 1 =R 1 ' and when Y is OH, R 1 =R 1 '-O- and when Y is -CH=CH2, R 1 =R 1’ When -CH=CH- and Y is -C≡CH, R 1 =R 1’ -C≡C- and R 1 , R 2 is the above-mentioned R 1 , R 2 ]

[0007] According to another aspect of the present invention, there is provided a resist composition comprising a resin component and an acid generator, wherein the acid generator is the above-mentioned sulfonate-based photoacid generator.

[0008] According to another aspect of the present invention, there is provided a patterning method comprising the steps of mixing the aforementioned resist composition, forming a film, and patterning the film.

[0009] Another aspect of the present invention provides uses of the resist composition described above, including the use of the resist composition in the production of protective films for electronic components, interlayer insulating materials, and pattern transfer materials.

[0010] By applying the technical scheme of the present invention, the present application provides a sulfonate-based photoacid generator having general formula I, which contains a sulfonate group in its molecule, and the sulfonate group is directly linked to an imide structure, which has photodegradable properties and can cleave an NO bond to generate different types of sulfonic acids upon irradiation with active energy rays. The active energy rays are active energy rays with wavelengths of 300 to 450 nm in the near-ultraviolet and visible light regions, and have high sensitivity and strong absorption, particularly for active energy rays with a wavelength of 365 nm (i-rays). When a resist composition containing the sulfonate-based photoacid generator and a resin component is dissolved in an alkaline developer and applied to a photosensitive composition exposed to light, the photosensitivity of the sulfonate-based photoacid generator is improved, allowing the formation of patterns with excellent sensitivity and good contrast, and even when attempting to form fine patterns, sufficiently high resolution and sensitivity can be achieved. Furthermore, the sulfonate-based photoacid generator of the present invention contains an epoxy group structure in its substituent, and is capable of ring-opening under acidic, high-temperature conditions but not under neutral, high-temperature conditions. This is advantageous in that it reduces the amount of auxiliary agent used in the resist, reduces the diffusion of photoacid molecules, and improves the robustness of lithography patterns. DETAILED DESCRIPTION OF THE INVENTION

[0011] In addition, unless there is a contradiction, the embodiments and features of the embodiments in the present application may be combined with each other. The present invention will be described in detail below with reference to the combined embodiments.

[0012] As analyzed in the Background Art section, the prior art has problems such as acid migration and poor robustness of lithography patterns. To solve these problems, the present invention provides a sulfonate-based photoacid generator, a method for producing the same, a patterning method, a resist composition, and uses thereof.

[0013] In one exemplary embodiment of the present application, there is provided a sulfonate-based photoacid generator having the following general formula (I): [ka] [In the formula, R 1 is a substituted or unsubstituted C2 to C 25 Hydrocarbon groups, substituted or unsubstituted C2-C 25 Alkoxy groups, substituted or unsubstituted C2-C 25 In particular, -CH2- may be substituted by -O-, -S-, -CO-, -O-CO- or -COO-, and in particular, a C atom may be substituted by an N atom, and a substituted or unsubstituted C2 to C6 alkylthio group is 25 Hydrocarbon groups, substituted or unsubstituted C2-C 25 Alkoxy groups, substituted or unsubstituted C2-C 25 At least one substituted or unsubstituted C2-C alkylthio group at the end of the alkylthio group 10 containing an epoxy group of R 2 is C1~C 20 Alkyl groups of C6 to C 18 is any one selected from the group consisting of a substituted or unsubstituted aryl group of the formula (I), a camphoryl group, a camphorquinone group, and an azidonaphthalenone group.]

[0014] In the present application, a sulfonate-based photoacid generator having general formula I contains a sulfonate group in its molecule, and the sulfonate group is directly linked to an imide structure, which has photodegradable properties and can cleave an NO bond to generate different types of sulfonic acids upon irradiation with active energy rays. The active energy rays are active energy rays with wavelengths of 300 to 450 nm in the near-ultraviolet and visible light regions, and have high sensitivity and strong absorption, particularly for active energy rays with a wavelength of 365 nm (i-line). When a resist composition containing the sulfonate-based photoacid generator and a resin component is dissolved in an alkaline developer and applied to a photosensitive composition exposed to light, the improved photosensitivity of the sulfonate-based photoacid generator enables the formation of patterns with excellent sensitivity and good contrast, and even when attempting to form fine patterns, sufficiently high resolution and sensitivity can be achieved. Furthermore, the sulfonate-based photoacid generator of the present invention contains an epoxy group structure in the substituent, and is capable of ring-opening under acidic and high-temperature conditions but does not ring-open under neutral and high-temperature conditions. This is advantageous in that it reduces the amount of auxiliary agent used in the resist, reduces the diffusion of photoacid molecules, and improves the robustness of lithography patterns.

[0015] In one embodiment of the present application, substituted or unsubstituted C2 to C 25 The hydrocarbon group is a substituted or unsubstituted C2-C 25 Straight chain alkyl groups, substituted or unsubstituted C3-C 25 Branched chain alkyl groups, substituted or unsubstituted C4-C 25 Alkenyl groups, substituted or unsubstituted C4-C 25 and preferably, R 1 is a substituted or unsubstituted C6-C 17 Branched chain alkyl groups, substituted or unsubstituted C9-C 16 Alkenyl groups, substituted or unsubstituted C9-C 18 Alkynyl groups, substituted or unsubstituted C6-C 17 Alkoxy groups, substituted or unsubstituted C6-C 15 and More preferably, substituted or unsubstituted C6 to C 17 The branched chain alkyl group is [ka] and preferably, a substituted or unsubstituted C9 to C 16 The alkenyl group is [ka] and preferably, a substituted or unsubstituted C9 to C 18 The alkynyl group is [ka] and preferably, a substituted or unsubstituted C6 to C 17 The alkoxy group is [ka] and preferably, a substituted or unsubstituted C6 to C 15 The alkylthio group is [ka] where "*" is selected from the group consisting of R 1 and the naphthalene ring of the sulfonate-based photoacid generator.

[0016] In order to more easily synthesize the sulfonate-based photoacid generator and to achieve cost-effectiveness, it is preferable to use a compound represented by the formula: R 1 is a substituted or unsubstituted C9-C 16 Alkenyl groups, substituted or unsubstituted C9-C 18 Alkynyl groups, substituted or unsubstituted C6-C 17 In consideration of the fact that alkenyl groups tend to yellow, it is more preferable for transparent systems to use alkoxy groups such as R 1 is a substituted or unsubstituted C9-C18 Alkynyl groups, substituted or unsubstituted C6-C 17 The alkoxy group is any one selected from the group consisting of:

[0017] In one embodiment of the present application, the epoxy group is a C2 to C5 epoxy group, and preferably, the epoxy group is [ka] and more preferably, [ka] is.

[0018] The number of ring-forming carbon atoms in the epoxy group affects the degree of difficulty in ring-opening, and the preferred epoxy groups are more advantageous in improving the ring-opening ability of the sulfonate-based photoacid generator under acidic, high-temperature conditions.

[0019] In order to further improve the structural stability and performance of the sulfonate-based photoacid generator, it is preferable to use the above-mentioned R 2 In C1~C 20 The alkyl group is a substituted or unsubstituted C1-C 20 Straight chain alkyl groups, substituted or unsubstituted C3-C 20 Branched chain alkyl groups, substituted or unsubstituted C3-C 20 and preferably, R 2 is C1~C 10 Alkyl groups of C6 to C 10 substituted or unsubstituted aryl groups, substituted or unsubstituted C3-C 10 is any one selected from the group consisting of a cycloalkyl group, a camphoryl group, a camphorquinone group, and an azidonaphthalenone group, and more preferably, R 2is any one selected from the group consisting of a substituted or unsubstituted C1 to C8 linear alkyl group, a substituted or unsubstituted C3 to C8 branched alkyl group, a substituted or unsubstituted C3 to C5 cycloalkyl group, a substituted or unsubstituted phenyl group, a camphoryl group, a camphorquinone group, and an azidonaphthalenone group, and more preferably, R 2 The substituent in is a halogen atom, more preferably a fluorine atom, and even more preferably R 2 is any one selected from the group consisting of a C1-C4 linear perfluoroalkyl group, a C1-C4 linear alkyl group, a C3-C6 branched perfluoroalkyl group, a perfluorophenyl group, a phenyl group substituted with a C1-C4 perfluoroalkyl group, a phenyl group substituted with a C1-C4 alkyl group, a camphoryl group, a camphorquinone group, and an azidonaphthalenone group, and preferably R 2 is any one selected from the group consisting of a trifluoromethyl group, a perfluorobutyl group, an n-propyl group, an n-butyl group, a camphoryl group, a p-tolyl group, and an o-trifluoromethylphenyl group.

[0020] In some embodiments of the present application, the structural formula of the sulfonate-based photoacid generator is preferably: [ka] [ka] [ka] [ka] The compound is any one or more selected from the group consisting of:

[0021] In another exemplary embodiment of the present application, there is provided a method for preparing the aforementioned sulfonate-based photoacid generator, the method comprising: 1' a step S1 of reacting compound 2 with Y to form compound 2; a step S2 of reacting compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to form a hydroxylamine compound; and a step S3 of reacting the hydroxylamine compound with R 2 SO2X 2 or (R 2 and step S3 of esterifying the compound with SO2)2O to obtain a sulfonate-based photoacid generator. The structural formulas of Compound 1 and Compound 2 are as follows: [ka] [In the formula, X 1 represents any one selected from the group consisting of -H, -OH, -SH, and a halogen atom; Y represents any one selected from the group consisting of -OH, -CH=CH2, -C≡CH, and a halogen atom; X 2 is a halogen atom, and R 1 'Y is X in compound 1 1 React with the substituent R 1 When Y is a halogen atom, R 1 =R 1 ' and when Y is OH, R 1 =R 1 '-O- and when Y is -CH=CH2, R 1 =R 1’ When -CH=CH- and Y is -C≡CH, R 1 =R 1’ -C≡C- and R 1 , R 2 is the aforementioned R 1 , R 2 ]

[0022] In the above step S1, naphthalic anhydride (compound 1) substituted at the 4-position is converted to a naphthalic anhydride (compound 2) substituted at the terminal R 1 'Y (halogenated hydrocarbon, alkene, alkyne, alcohol, etc.) and R at the 4-position by different types of reactions such as Friedel-Crafts reaction, Heck coupling reaction, addition reaction, or Click reaction. 1substituted naphthalic anhydride (compound 2), where R 1 Y may be commercially available or may be produced by reactions such as esterification, etherification, and addition between a primary alcohol, a carboxylic acid, a terminal olefin, a terminal alkyne, and a halogenated hydrocarbon. In step S2, the 4-position is R 1 The hydroxylamine-substituted naphthalic anhydride is subjected to a hydroxylamination reaction with a hydroxylamination reagent under alkaline or acidic conditions to produce a hydroxylamine compound. The hydroxylamination reagent may be hydroxylamine sulfate or hydroxylamine hydrochloride. Controlling the hydroxylamination reaction temperature between 25 and 100°C, more preferably between 75 and 100°C, is advantageous for improving the efficiency of the hydroxylamination reaction. In step S3, the hydroxylamine compound and the acylating reagent are esterified in an inert solvent under alkaline conditions to produce a sulfonate compound. Controlling the esterification reaction temperature between -10 and 60°C, more preferably between 0 and 25°C, is advantageous for improving the efficiency of the esterification reaction.

[0023] Furthermore, all of the raw materials and reagents used in the above-described preparation methods are compounds known in the art and may be obtained commercially or may be conveniently prepared by known processes, the details of which will not be described here.

[0024] The sulfonate-based photoacid generator of the present invention can be applied to any known application of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, resists for MEMS, materials for stereolithography and microstereolithography, etc. In particular, as a photoacid generator in a resist composition, it can be used in semiconductor lithography by producing a resist together with a resin having an acid-dissociable group.

[0025] In another exemplary embodiment of the present application, there is provided a resist composition comprising a resin component and the above-described sulfonate-based photoacid generator.

[0026] The resist composition of the present invention may be divided into positive-working and negative-working compositions depending on the application. In addition to a sulfonate-based photoacid generator, a positive-working composition generally contains a resin component (B1) that becomes highly soluble in an alkaline developer under the action of acid. During the composition pattern formation process, selective exposure causes the acid-labile groups in the positive-working resin in the exposed region to be deprotected by the action of the acid generated by the photoacid generator, making them soluble in an alkaline developer. Therefore, during alkaline development, the pattern in the unexposed region remains, forming a positive pattern. Unlike positive-working compositions, negative-working compositions use a resin-crosslinker component (B2) that crosslinks under the action of acid and is insoluble in an organic developer. In the exposed region, the resin reacts with the crosslinker under the catalytic action of the acid generated by the photoacid generator to form a polymer that is insoluble in an organic developer, which remains, while the unexposed region is dissolved and removed by the organic developer, finally forming a negative pattern. However, for the specific resin component (B1) and resin-crosslinker component (B2), reference may be made to the specific contents disclosed in paragraphs

[0046] to

[0076] of the specification of the Chinese patent application with application number 202011299973.1, but further description thereof is omitted here.

[0027] In the positive / negative resist composition of the present invention, the sulfonate-based photoacid generator generates sulfonic acid by cleaving the NO bond upon irradiation with active energy rays, and the PEB process can achieve a difference in solubility in a developer between the exposed and unexposed regions. The sulfonate-based photoacid generator product may be used alone or in combination of multiple types.

[0028] Due to the performance of the sulfonate-based photoacid generator having general formula I in the present application, when a resist composition containing the sulfonate-based photoacid generator and a resin component is dissolved in an alkaline developer and used in an exposed photosensitive composition, sufficiently high resolution and sensitivity can be achieved even when attempting to form a fine pattern. Furthermore, the amount of auxiliary agents used in the resist can be reduced, which reduces the diffusion of photoacid molecules and improves the robustness of the lithography pattern.

[0029] In one embodiment of the present application, the resin component has an acid labile group protected by a protecting group, and the acid labile group is at least one selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group. The content of the acid labile group preferably accounts for 1 to 80%, and more preferably 3 to 70%, of the resin component content. The protecting group preferably includes at least one of groups represented by the following formula (a) or formula (b): [ka] [wherein, in formula (a), R 3 is a substituted or unsubstituted C1 to C 20 Straight chain alkyl groups, substituted or unsubstituted C3-C 20 Branched chain alkyl groups, substituted or unsubstituted C3-C 20 and preferably, R 3 is a substituted or unsubstituted C1 to C 10 Straight chain alkyl groups, substituted or unsubstituted C3-C 10 Branched chain alkyl groups, substituted or unsubstituted C3-C 10 and more preferably, R 3 is any one or more selected from the group consisting of substituted or unsubstituted C1 to C6 linear alkyl groups, substituted or unsubstituted C3 to C6 branched alkyl groups, and substituted or unsubstituted C3 to C6 cycloalkyl groups, and preferably, R 3 When a substituent is present in R, the substituent is any one or more selected from the group consisting of a halogen, a hydroxyl group, a cyano group, a C1-C4 linear alkyl group, and a C3-C5 branched alkyl group, and preferably the substituent is any one or more selected from the group consisting of a fluorine atom, a methyl group, and an ethyl group, and preferably R 3 One or more C atoms in may be replaced by any heteroatom of O, S, N or Si, more preferably R 3represents a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a t-butoxy group, a benzyloxy group, a 1-methoxyethoxy group, a 1-ethoxyethoxy group, [ka] In formula (b), R 4 is a substituted or unsubstituted C1 to C 20 Straight chain alkyl groups, substituted or unsubstituted C3-C 20 Branched chain alkyl groups, substituted or unsubstituted C3-C 20 and n is 0 or 1, and preferably R 4 is a substituted or unsubstituted C1 to C 10 Straight chain alkyl groups, substituted or unsubstituted C3-C 10 Branched chain alkyl groups, substituted or unsubstituted C3-C 10 and more preferably, R 4 is any one or more selected from the group consisting of substituted or unsubstituted C1 to C6 linear alkyl groups, substituted or unsubstituted C3 to C6 branched alkyl groups, and substituted or unsubstituted C3 to C6 cycloalkyl groups, and more preferably, R 4 is one or more selected from the group consisting of a t-butoxycarbonyl group, a propoxycarbonyl group, an adamantyloxycarbonyl group, and a t-butoxycarbonylmethyl group.

[0030] Preferably, the above-mentioned type of resin component is advantageous in synergism with the sulfonate-based photoacid generator, and robust lithographic patterns can be obtained.

[0031] The amount of the acid generator used may refer to the amount of acid generators generally used in the prior art. In one embodiment, the weight content of the acid generator is 0.5 to 5%, preferably 1 to 3%, relative to the mass of the solid content of the resist composition, thereby achieving good photosensitivity and improving the development effect.

[0032] The solvent dissolves each component in the resist composition to form a uniform solution, and adjusts the viscosity and coatability of the solution, which is advantageous for film formation. For specific solvents, reference may be made to the Chinese patent application with application number 202011299973.1. Alternatively, the resist composition may further contain auxiliary agents commonly used in the art, but the description thereof will be omitted here.

[0033] In another exemplary embodiment of the present application, there is provided a patterning method including the steps of mixing, depositing, and patterning the above-described resist composition.

[0034] When applying the resist composition of the present invention, first, a resin solution dissolved or dispersed in an organic solvent is applied to a substrate, for example, by spin coating, and then the substrate is heated to volatilize the solvent, thereby forming a resist film on the substrate. Thereafter, the resist film is irradiated with light in the shape of a wiring pattern (i.e., exposed to light), and then post-exposure bake (PEB) is performed, followed by alkaline development, thereby forming a wiring pattern.

[0035] The drying conditions for the resin solution after application vary depending on the solvent used, but are preferably carried out at 50 to 150°C for 1 to 30 minutes, i.e., are appropriately determined depending on the amount of solvent remaining after drying (mass %), etc.

[0036] After forming a resist film on the substrate, the wiring pattern is irradiated with light. For light irradiation, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electron beam irradiation device, an X-ray irradiation device, a laser device (e.g., an argon laser, a dye laser, a nitrogen laser, an LED, a helium-cadmium laser device), etc. may be used, and a high-pressure mercury lamp and an LED lamp are preferably used.

[0037] The temperature for post-exposure bake (PEB) is usually 40 to 200°C, preferably 60 to 150°C. If the temperature is below 40°C, the deprotection reaction or crosslinking reaction cannot be carried out sufficiently, resulting in an insufficient difference in solubility between the exposed and unexposed areas and making it impossible to form a pattern. If the temperature exceeds 200°C, there is a problem of reduced productivity. The heating time is usually 0.5 to 30 minutes.

[0038] The development is performed with an alkaline developer, and the alkaline development method involves using an alkaline developer. The alkaline developer may be selected from the group consisting of 0.1 to 10% (by mass) aqueous solutions of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate, and the alkaline developer may contain a water-soluble organic solvent such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, etc. The development method may be selected from a dipping method, a shower method, and a spray method, and is preferably a spray method. The temperature of the developer used is preferably 25 to 40°C, and the development time is appropriately determined depending on the film thickness of the resist film, and finally a pattern corresponding to the mask is obtained.

[0039] Another exemplary embodiment of the present application provides uses of the resist composition described above, including use of the resist composition in the manufacture of protective films for electronic components, interlayer insulating materials, and pattern transfer materials.

[0040] Specifically, the above uses may include forming an interlayer insulating film using the resist composition and using it in TFTs and panels of liquid crystal displays, or using it as a protective film for color filters and spacer pillars, or even using it as a PS photoresist or BCS photoresist for pattern transfer.

[0041] The electronic components include, but are not limited to, liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED, and quantum dot LED display devices.

[0042] The beneficial effects of the present invention will be explained below in combination with specific examples.

[0043] (Example of Preparation of Sulfonate-Based Photoacid Generator) Example 1 [ka] Under nitrogen gas protection, a 500 mL four-neck flask was charged with 200 g of toluene, 27.71 g of 4-bromo-1,8-naphthalic anhydride (S1), 20.49 g of 3-ethyl-3-((2-(vinyl)ethoxy)methyl)oxetane, 0.22 g of palladium acetate, 0.52 g of triphenylphosphine, and 11.13 g of triethylamine. The mixture was stirred and heated to 75-80 °C, and the temperature was maintained for 6 h. After stopping the stirring and cooling to room temperature, 100 mL of n-hexane was added, stirred for 0.5 h, filtered, and the filter cake was rinsed once with 20 g of toluene. The organic phases were combined. The solvent was removed under reduced pressure, and the mixture was dissolved in 100 g of DCM. 3 g of activated carbon was added, stirred, and decolorized. After removing the solvent, 30.10 g of intermediate T1-1 was obtained by column chromatography.

[0044] A 250 mL four-neck flask was charged with 100 g of water, 19.12 g of intermediate T1-1, 4.17 g of hydroxylamine hydrochloride, and 4.63 g of ammonium acetate, and the mixture was stirred and heated to 75-80°C. The temperature was maintained and the reaction was carried out for 3 hours. The stirring was stopped, the mixture was cooled slightly, and then filtered while still hot. The filtered solid was rinsed with approximately 100 g of pure water and dried in an oven to obtain 13.95 g of intermediate T1-2 as a pale yellow solid.

[0045] Under nitrogen gas protection, 200 g of dichloromethane, 13.95 g of intermediate T1-2, and 3.33 g of pyridine were added to a 250 mL four-neck flask and stirred uniformly. The temperature was then lowered to 0-5°C, and 11.88 g of trifluoromethanesulfonic anhydride was gradually added dropwise. The mixture was stirred for 3 hours while maintaining the temperature. 50 g of purified water was added, and the mixture was stirred for 0.5 hours. The liquids were separated, and the organic phase was concentrated at 55°C and atmospheric pressure until no distillate remained. 50 g of n-hexane was added to crystallize the mixture, yielding 15.25 g of sulfonate-based photoacid generator 34 as a pale yellow solid.

[0046] Example 2 [ka] A 500 mL four-neck flask was charged with 250 g of tetrahydrofuran, 19.82 g of 1,8-naphthalic anhydride, 26.66 g of aluminum chloride, and 16.15 g of 3-ethyl-3-(chloromethyl)-oxetane. The mixture was stirred until uniform, then heated to 70 °C and refluxed for 12 hours. Stirring was stopped, the system was cooled to room temperature, the solvent was removed in vacuo, 100 g of purified water and 150 g of dichloromethane were added, and the mixture was shaken uniformly to separate the layers. The organic phase was concentrated to obtain 15.56 g of intermediate T2-1 as a white solid.

[0047] For the preparation of T2-2 and photoacid 1, the second and third reactions in Example 1 can be referred to.

[0048] Example 3 [ka] For the method of producing the sulfonate-based photoacid generator 28, see Example 1.

[0049] Example 4 [ka] A 250 mL stainless steel autoclave was charged with 150 g of methanol, 17.62 g of intermediate T3-1, 0.15 g of 5% Pd / C catalyst, and 0.5 mL of acetic acid. After leak detection and sealing, the autoclave was filled with hydrogen gas at 1-2 MPa, stirred, and heated to 55-65°C. The temperature was maintained for 6 hours. Stirring was stopped and the temperature was lowered to room temperature. After filtration and removal of the solvent under reduced pressure, the mixture was dissolved in 100 g of DCM, 3 g of activated carbon was added, and the mixture was decolorized by stirring. After removal of the solvent, 16.35 g of intermediate T4-1 was obtained as a white solid by column chromatography.

[0050] For the production of T4-2 and sulfonate-based photoacid generator 8, the second and third reactions in Example 1 can be referred to.

[0051] Example 5 [ka]

[0052] Under nitrogen gas protection, 200 g of 3-ethyl-3-oxetanemethanol, 27.71 g of 4-bromonaphthalic anhydride, 41.46 g of potassium carbonate, and 0.67 g of anhydrous cupric chloride were added to a 500 mL four-neck flask and stirred at reflux for 12 h. After heating, the mixture was returned to room temperature and filtered. 500 g of n-hexane was added to the filtrate and stirred at 0 °C for 0.5 h to allow crystallization. The filter cake was collected and rinsed with 20 mL of n-hexane. The filter cake was dissolved in a small amount of DCM and purified by column chromatography after filtration, finally yielding 21.55 g of intermediate T5-1 as a white solid.

[0053] For the production of T5-2 and sulfonate-based photoacid generator 15, the second and third reactions in Example 1 can be referred to.

[0054] Example 6 [ka] Under nitrogen gas protection, 20 g of 3-ethyl-3-oxetanemethanol and 200 mL of THF were added to a 500 mL four-neck flask, stirred uniformly, and then cooled to 0°C. A total of 4.80 g of NaH was added in multiple portions, and the reaction temperature was controlled to less than 5°C. After stirring uniformly, the temperature was maintained at 0°C, and 17.07 g of propargyl bromide was gradually added dropwise to the reactor. After the addition was completed, the temperature was gradually raised to room temperature and the reaction was allowed to proceed for 3 hours. The reaction was stopped, and the reaction solution was filtered, concentrated, and purified by column chromatography to obtain 15.20 g of 3-ethyl-3-oxetanol propargyl ether.

[0055] Under nitrogen gas protection, 18.50 g of 3-ethyl-3-oxetanol propargyl ether, 27.71 g of 4-bromonaphthalic anhydride, and 300 mL of THF were added to a 500 mL four-neck flask and stirred until uniform. Then, 0.95 g of cuprous iodide, 2.62 g of triphenylphosphine, 0.70 g of bis(triphenylphosphine)palladium dichloride, and 20.24 g of triethylamine were added. The mixture was heated to 70 °C and stirred for 3 h. After heating, the mixture was cooled to room temperature and concentrated to remove the solvent. The mixture was purified by column chromatography to finally obtain 29.78 g of intermediate T6-1 as a pale yellow solid.

[0056] For the production of T6-2 and sulfonate-based photoacid generator 35, the second and third reactions in Example 1 can be referred to.

[0057] Example 7 [ka]

[0058] For the production of T6-1 and T6-2, see Example 6.

[0059] A 500 mL four-neck flask was charged with 18.27 g of T6-2 and 200 mL of dichloromethane. The mixture was stirred to dissolve, and then 7.59 g of triethylamine was added. The temperature was lowered to 0 °C and pre-cooled for 15 min. A total of 10.49 g of p-toluenesulfonyl chloride was added to the reactor in multiple batches, and the system temperature was controlled below 5 °C. After stirring and reacting for 3 h, 100 mL of aqueous ammonia was gradually added to the system. After the system stabilized, the liquids were separated. The organic phase was washed with 50 mL of 0.5 M hydrochloric acid and then twice with purified water (100 mL each time). The organic phase was concentrated until a solid precipitated, and 200 mL of n-hexane was added and stirred to crystallize. After filtration and drying, 20.00 g of a pale yellow solid was obtained, which was sulfonate-based photoacid generator 50.

[0060] Example 8 [ka]

[0061] For the preparation of T6-1 and T6-2, see Example 6. For the preparation of sulfonate-based photoacid generator 52, see Example 7, except that p-toluenesulfonyl chloride was replaced with butanesulfonyl chloride as a raw material.

[0062] By referring to the reaction processes similar to those in Examples 1 to 8, the materials in Examples 9 to 21 were respectively replaced and the reaction conditions were appropriately adjusted to obtain other corresponding sulfonate-based photoacid generators 2, 11, 13, 14, 18, 21, 24, 25, 27, 29, 32, 36, and 39, respectively.

[0063] Example 22 For the preparation of sulfonate photoacid generator 49, see Example 7, substituting suspended camphorsulfonyl chloride for p-toluenesulfonyl chloride as the starting material.

[0064] Example 23 For the preparation of sulfonate-based photoacid generator 51, reference can be made to Example 7, where p-toluenesulfonyl chloride was replaced with propanesulfonyl chloride as the raw material.

[0065] Example 24 For the preparation of sulfonate-based photoacid generator 53, reference can be made to Example 7, where p-toluenesulfonyl chloride was replaced with 2-(trifluoromethyl)benzenesulfonyl chloride as the raw material.

[0066] The numbers of the sulfonate-based photoacid generators prepared in all examples and 1 The results of the 1 H NMR evaluation are shown in Table 1.

[0067] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4]

[0068] (Performance evaluation) The performance of each of the sulfonate-based photoacid generators synthesized in Examples 1 to 24 and the sulfonate-based photoacid generator of Comparative Example 1 was evaluated, and the evaluation indexes included molar absorption coefficient, solubility, and chemical stability.

[0069] (1) Molar absorption coefficient The compound was diluted to 0.25 mmol / L using acetonitrile, and the absorbance was measured in a 1 cm cell length in the range of 200 to 600 nm using a UV-visible spectrophotometer (UPG-752). The molar extinction coefficient ε at each wavelength, i.e., ε (L mol -1 ·cm -1 ) = A / (0.00025 mol / L × 1 cm), where A represents the absorbance at each wavelength.

[0070] (2)Solubility High solubility not only facilitates purification of the photoacid generator compound, but also allows the photoacid generator compound to be used in a wider concentration range in photoresists and different solvent systems. 1.0000 g of the photoacid generator compound product was taken, and at 25°C, solvent was gradually added to each test tube until all of the solids in the test tube were dissolved. The mass of the solvent used was recorded, and the solubility was calculated as (1 g / mass of solvent) × 100%. The evaluation results are shown in Table 2.

[0071] [Table 2] Among them, the non-ionic photoacid generator of Comparative Example 1 [ka] and is written as A*1.

[0072] As can be seen from the measurement results in Table 2, the photoacid generator of the present invention has a high molar absorption coefficient at 365 nm, has strong light absorption ability, can fully utilize light energy, can ensure high utilization rate in resist use, and exhibits good solubility.

[0073] (Examples of Resist Compositions) Referring to the compositions of resist composition examples 1 to 31 and resist composition comparison examples 1 to 6 in Table 3, each raw material was uniformly dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain a resist composition with a solids concentration of approximately 20% (mass %). Among these, the component types and contents of the sulfonate-based photoacid generator (A), resin component (B), and acid binder triethylamine (C) are shown in Table 3.

[0074] Composition Example 1 As the resin component (B), one type of resin is used, and the formula B 11 , formula B 12 and Formula B 13 The numerical value at the bottom right of each repeating unit indicates the content (mass%) of that repeating unit in the resin. The weight-average molecular weight of B1 resin is approximately 10,000. [ka] The sulfonate-based photoacid generator (A) is the sulfonate-based photoacid generator of Example 1.

[0075] Composition Examples 2 to 24 The composition differs from Example 1 in that the sulfonate-based photoacid generators of Examples 2 to 24 are used in this order as the sulfonate-based photoacid generator (A). The types and contents of the remaining components are shown in Table 3.

[0076] Composition Example 25 Two types of resin are used as the resin component (B), and the formula B 21 , formula B 22 and Formula B 23The difference from composition Example 5 is that it is composed of the repeating units shown in the table below, and the number to the right of each repeating unit indicates the content (mass%) of that repeating unit in the resin. The weight-average molecular weight of B2 resin is approximately 10,000. [ka]

[0077] Composition Example 26 Three types of resin are used as the resin component (B), and the formula B 31 and Formula B 32 The difference from composition Example 5 is that it is composed of the repeating units shown in the table below, and the number to the right of each repeating unit indicates the content (mass%) of that repeating unit in the resin. The weight-average molecular weight of B3 resin is approximately 10,000. [ka]

[0078] (Composition Examples 27-28) The composition differs from Example 5 in that the content of the sulfonate-based photoacid generator is different.

[0079] Composition Example 29 Composition Example 5 differs in that no acid binder was added.

[0080] Composition Example 30 Composition Example 6 differs in that no acid binder was added.

[0081] Composition Example 31 Composition Example 7 differs in that no acid binder was added.

[0082] (Comparative Composition Example 1) The composition differs from Example 5 in that the sulfonate-based photoacid generator A*1 of Comparative Example 1 was used.

[0083] (Comparative Composition Example 2) The composition differs from Example 6 in that the sulfonate-based photoacid generator A*1 of Comparative Example 1 was used.

[0084] (Comparative Composition Example 3) The composition differs from Example 7 in that the sulfonate-based photoacid generator A*1 of Comparative Example 1 was used.

[0085] (Comparative Composition Example 4) The composition differs from Comparative Example 1 in that no acid binder was added.

[0086] (Comparative Composition Example 5) The composition differs from Comparative Example 2 in that no acid binder was added.

[0087] (Comparative Composition Example 6) The composition differs from Comparative Example 3 in that no acid binder was added.

[0088] The resist compositions produced in Composition Examples 1 to 31 and Composition Comparative Examples 1 to 6 were evaluated for photosensitivity and resolution by the following methods, and the results are recorded in Table 3.

[0089] (1) Photosensitivity evaluation The resist composition of each example and comparative example was applied to each silicon wafer to a thickness (1 μm) that would allow for pattern formation, forming a coating film. The formed coating film was prebaked at 90°C for 100 seconds. After prebaking, the coating film was exposed to light using a mask for forming a 10 μm diameter hole pattern while changing the exposure dose (exposure wavelength 365 nm), and then developed at 25°C for 30 seconds using a 2.0% aqueous solution of tetramethylammonium hydroxide. Using the above method, the minimum exposure value required for forming a 10 μm diameter hole pattern was determined. Sensitivity was evaluated based on the obtained minimum exposure value according to the following criteria: "Good" indicates a photosensitivity of -50 mJ / cm 2 "×" indicates a photosensitivity of -300 mJ / cm or less. 2 Indicates that it is equal to or greater than this.

[0090] (2) Resolution evaluation A mask was used to form a hole pattern with a diameter of 5 μm, and the irradiation was 100 mJ / cm 2 In addition to exposing at an exposure dose of 1000 ppm, the coating film was formed, exposed, and developed in the same manner as in the photosensitivity evaluation. The coating film after development was observed, and the resolution was evaluated based on the following criteria: "○" indicates that a pattern with a diameter of 5 μm could be formed, and "○" indicates that a pattern with a diameter of 5 μm could not be formed.

[0091] [Table 3]

[0092] As can be seen from the results in Table 3, the resist compositions of Examples 1 to 28 of the present invention have excellent photosensitivity and resolution, far superior to those of Comparative Examples 1 to 3. As shown in Examples 29 to 31 of the compositions, the resolution is excellent even when no acid binder is added, but Comparative Examples 4 to 6 of the compositions to which no acid binder is added similarly show average resolution.

[0093] As can be seen from the above description, the above-described embodiments of the present invention achieve the following technical effects.

[0094] In the present application, a sulfonate-based photoacid generator having general formula I contains a sulfonate group in its molecule, and the sulfonate group is directly linked to an imide structure, which has photodegradable properties and can cleave an NO bond to generate different types of sulfonic acids upon irradiation with active energy rays. The active energy rays are active energy rays with wavelengths of 300 to 450 nm in the near-ultraviolet and visible light regions, and have high sensitivity and strong absorption, particularly for active energy rays with a wavelength of 365 nm (i-rays). When a resist composition containing the sulfonate-based photoacid generator and a resin component is dissolved in an alkaline developer and applied to an exposed photosensitive composition, the photosensitivity of the sulfonate-based photoacid generator is improved, allowing the formation of patterns with excellent sensitivity and good contrast, and even when attempting to form fine patterns, sufficiently high resolution and sensitivity can be achieved. Furthermore, the sulfonate-based photoacid generator of the present invention contains an epoxy group structure in its substituent, and is capable of ring-opening under acidic, high-temperature conditions but not under neutral, high-temperature conditions. This is advantageous in that it reduces the amount of auxiliary agent used in the resist, reduces the diffusion of photoacid molecules, and improves the robustness of lithography patterns.

[0095] The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and those skilled in the art will recognize that the present invention may have various modifications and variations. Any amendments, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims

1. A sulfonate-based photoacid generator characterized by having the following general formula (I): 【Chemical 1】 [In the formula, R １ is a substituted or unsubstituted C ２ ~C ２５ a hydrocarbon group of substituted or unsubstituted C ２ ~C ２５ an alkoxy group of the formula ２ ~C ２５ Among these, —CH ２ - may be substituted by -O-, -S-, -CO-, -O-CO- or -COO-, and among these, a C atom may be substituted by an N atom, and the substituted or unsubstituted C ２ ~C ２５ the hydrocarbon group represented by the formula (I), the substituted or unsubstituted C ２ ~C ２５ the substituted or unsubstituted C ２ ~C ２５ At least one substituted or unsubstituted C ２ ~C １０ Contains epoxy groups. R ２ is C １ ~C ２０ alkyl group of C ６ ~C １８ is any one selected from the group consisting of a substituted or unsubstituted aryl group represented by the formula (I), a camphoryl group, a camphorquinone group, and an azidonaphthalenone group.]

2. The substituted or unsubstituted C ２ ~C ２５ The hydrocarbon group is a substituted or unsubstituted C ２ ~C ２５ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ２５ branched alkyl groups of the formula ４ ~C ２５ an alkenyl group of the formula ４ ~C ２５ and Preferably, the R １ is a substituted or unsubstituted C ６ ~C １７ branched alkyl groups of the formula ９ ~C １６ an alkenyl group of the formula ９ ~C １８ an alkynyl group of the formula ６ ~C １７ an alkoxy group of the formula ６ ~C １５ and More preferably, the substituted or unsubstituted C ６ ~C １７ The branched chain alkyl group is 【Chemistry 2】 Any one selected from the group consisting of: Preferably, the substituted or unsubstituted C ９ ~C １６ The alkenyl group is 【Chemistry 3】 Any one selected from the group consisting of: Preferably, the substituted or unsubstituted C ９ ~C １８ The alkynyl group is 【Chemistry 4】 Any one selected from the group consisting of: Preferably, the substituted or unsubstituted C ６ ~C １７ The alkoxy group is 【Chemistry 5】 Any one selected from the group consisting of: Preferably, the substituted or unsubstituted C ６ ~C １５ The alkylthio group is 【Chemistry 6】 selected from the group consisting of However, "*" indicates the above R １ and is a linking site between the naphthalene ring of the sulfonate-based photoacid generator.

3. The epoxy group is C ２ ~C ５ Preferably, the epoxy group is 【Chemistry 7】 and more preferably, 【Chemistry 8】 2. The sulfonate-based photoacid generator according to claim 1, wherein

4. The R ２ In the above, １ ~C ２０ The alkyl group is a substituted or unsubstituted C １ ~C ２０ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ２０ branched alkyl groups of the formula ３ ~C ２０ is any one selected from the group consisting of cycloalkyl groups Preferably, the R ２ is C １ ~C １０ alkyl group of C ６ ~C １０ a substituted or unsubstituted aryl group represented by the formula: ３ ~C １０ a cycloalkyl group selected from the group consisting of a camphoryl group, a camphorquinone group, and an azidonaphthalenone group; More preferably, the R ２ is a substituted or unsubstituted C １ ~C ８ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ８ branched alkyl groups of the formula ３ ~C ５ a cycloalkyl group represented by the formula (I), a substituted or unsubstituted phenyl group, a camphoryl group, a camphorquinone group, and an azidonaphthalenone group; More preferably, the R ２ The substituent in is a halogen atom, more preferably a fluorine atom, Even more preferably, the R ２ is C １ ~C ４ a linear perfluoroalkyl group of C １ ~C ４ a straight chain alkyl group of C ３ ~C ６ a branched perfluoroalkyl group, a perfluorophenyl group, C １ ~C ４ a phenyl group substituted with a perfluoroalkyl group of the formula C １ ~C ４ and preferably, R ２ is any one selected from the group consisting of a trifluoromethyl group, a perfluorobutyl group, an n-propyl group, an n-butyl group, a camphoryl group, a p-tolyl group, and an o-trifluoromethylphenyl group.

5. The structural formula of the sulfonate-based photoacid generator is: 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 4. The sulfonate-based photoacid generator according to claim 1, wherein the sulfonate-based photoacid generator is one or more selected from the group consisting of:

6. A method for producing the sulfonate-based photoacid generator according to any one of claims 1 to 5, comprising the steps of: Compound 1 is R １ ' Step S1 of reacting with Y to produce compound 2; a step S2 of subjecting the compound 2 to a hydroxylamination reaction with hydroxylamine hydrochloride or hydroxylamine sulfate to produce a hydroxylamine compound; The hydroxylamine compound is ２ SO ２ X ２ or (R ２ SO ２ ) ２ a step S3 of esterifying the sulfonate-based photoacid generator with O; Including, A production method characterized in that the structural formulas of Compound 1 and Compound 2 are as follows: 【Chemistry 13】 [In the formula, X １ is any one selected from the group consisting of —H, —OH, —SH and a halogen atom, and Y is —OH, —CH═CH ２ , —C≡CH, and a halogen atom; ２ is a halogen atom, and R １ 'Y is X in compound 1 １ Reacts with the substituent to form R １ When Y is a halogen atom, R １ =R １ ', and when Y is OH, R １ =R １ '-O- and Y is -CH=CH ２ If R １ =R １’ When —CH≡CH— and Y is —C≡CH, R １ =R １’ -C≡C-, and R １ , R ２ is R according to any one of claims 1 to 5. １ , R ２ is the same as above.]

7. A resist composition comprising a resin component and the sulfonate-based photoacid generator according to any one of claims 1 to 5.

8. the resin component has an acid labile group protected by a protecting group, and the acid labile group is at least one selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group, and the content of the acid labile group preferably accounts for 1 to 80%, and more preferably 3 to 70%, of the content of the resin component; 8. The resist composition according to claim 7, wherein the protecting group preferably includes at least one of groups represented by the following formula (a) and formula (b): 【Chemistry 14】 [In formula (a), R ３ is a substituted or unsubstituted C １ ~C ２０ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ２０ branched alkyl groups of the formula ３ ~C ２０ and preferably, the R ３ is a substituted or unsubstituted C １ ~C １０ a straight chain alkyl group of substituted or unsubstituted C ３ ~C １０ branched alkyl groups of the formula ３ ~C １０ and more preferably, the R ３ is a substituted or unsubstituted C １ ~C ６ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ６ branched alkyl groups of the formula ３ ~C ６ and preferably, the R ３ When a substituent is present in the group, the substituent is selected from the group consisting of halogen, hydroxyl group, cyano group, C １ ~C ４ a straight chain alkyl group of C ３ ~C ５ Preferably, the substituent is one or more selected from the group consisting of a fluorine atom, a methyl group, and an ethyl group, and preferably, the R ３ One or more C atoms in may be replaced by any heteroatom of O, S, N or Si, and more preferably, ３ represents a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a t-butoxy group, a benzyloxy group, a 1-methoxyethoxy group, a 1-ethoxyethoxy group, 【Chemistry 15】 It is any one or more types selected from the group consisting of: [In the formula (b), R ４ is a substituted or unsubstituted C １ ~C ２０ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ２０ branched alkyl groups of the formula ３ ~C ２０ and n is 0 or 1, and preferably, ４ is a substituted or unsubstituted C １ ~C １０ a straight chain alkyl group of substituted or unsubstituted C ３ ~C １０ branched alkyl groups of the formula ３ ~C １０ and more preferably, the R ４ is a substituted or unsubstituted C １ ~C ６ a straight chain alkyl group of substituted or unsubstituted C ３ ~C ６ branched alkyl groups of the formula ３ ~C ６ and more preferably, the R ４ is one or more selected from the group consisting of a t-butoxycarbonyl group, a propoxycarbonyl group, an adamantyloxycarbonyl group, and a t-butoxycarbonylmethyl group.

9. 9. The resist composition according to claim 7, wherein the weight content of the acid generator is 0.01 to 5%, and preferably 0.1 to 3%, relative to the mass of the solid content of the resist composition.

10. The resist composition according to claim 7, wherein the weight content of the acid generator is 0.01 to 5%, and preferably 0.1 to 3%, relative to the mass of the solid content of the resist composition.

11. The resist composition according to claim 7, wherein the resist composition further contains a solvent.

10. A patterning method comprising the steps of mixing the resist composition according to any one of claims 7 to 9, forming a film, and patterning the film.

11. 10. Use of the resist composition according to any one of claims 7 to 9 in the production of a protective film for electronic components, an interlayer insulating material, or a pattern transfer material.

Images