WO2024041660A1 - Sulfonate-based photoacid generator, method for preparing same, method for patterning same, resist composition thereof, and use thereof - Google Patents

Abstract

The present invention provides a sulfonate-based photoacid generator, a method for preparing same, a method for patterning same, a resist composition thereof, and use thereof. The sulfonate-based photoacid generator is represented by general formula (I), wherein R¹ is selected from any one of a substituted or unsubstituted C₂ to C₂₅ hydrocarbyl, a substituted or unsubstituted C₂ to C₂₅ alkoxy, and a substituted or unsubstituted C₂ to C₂₅ alkylthio, wherein -CH₂- may be optionally substituted with -O-, -S-, -CO-, -O-CO-, or -COO-, C atoms may also be optionally substituted with an N atom, and the terminus of R¹ comprises at least one substituted or unsubstituted C₂ to C₁₀ oxacyclic group; R² is selected from any one of a C₁ to C₂₀ alkyl, a substituted or unsubstituted C₆ to C₁₈ aryl, camphoryl, camphorquinonyl, and nitrine naphthalenonyl. The sulfonate-based photoacid generator can reduce the diffusion of photoacid molecules and improve the firmness of photoetching patterns.

Description

Sulfonate photoacid generator and its preparation method, patterning method, resist composition and its application

This application is based on the Chinese application with CN application number 202211038021.3 and a filing date of August 26, 2022, and claims its priority. The disclosure content of the CN application is once again introduced into this application as a whole.

Technical field

The present invention relates to the technical field of photosensitive materials. Specifically, it relates to a sulfonate photoacid generator and its preparation method, patterning method, resist composition and application thereof.

Background technique

Photoacid generator is one of the key components of chemically amplified photoresist, and its structure and performance have a great impact on lithography images. With the development of the semiconductor industry, people's demand for high-definition patterns continues to grow. At the same time, there is also an expansion of the applicable types of photoacid generators, and the performance of photoacid generators, especially low diffusivity, high solubility, and high acid production. Characteristics such as efficiency put forward higher requirements. Although sulfonate compounds of naphthalene anhydride are widely known as photoinitiators in the semiconductor field, most current resist formulations require the addition of additives to inhibit acid migration or enhance pattern fastness.

Contents of the invention

The main purpose of the present invention is to provide a sulfonate photoacid generator and its preparation method, patterning method, resist composition and application thereof, so as to solve the problem of acid migration and photolithographic pattern fastness in the prior art. Bad question.

In order to achieve the above object, according to one aspect of the present invention, a sulfonate ester photoacid generator is provided. The sulfonate ester photoacid generator has the following general formula (I):

Wherein, R ¹ is selected from a substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group, a substituted or unsubstituted C ₂ to C ₂₅ alkoxy group, a substituted or unsubstituted C ₂ to C ₂₅ alkylthio group. Any one, in which -CH ₂ - can be optionally replaced by -O-, -S-, -CO-, -O-CO- or -COO-, and the C atom can also be optionally replaced by N atom Substituted, and the terminal of the substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group, the substituted or unsubstituted C ₂ to C ₂₅ alkoxy group, the substituted or unsubstituted C ₂ to C ₂₅ alkylthio group contains at least A substituted or unsubstituted C ₂ to C ₁₀ epoxy group; R ² is selected from a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₁₈ substituted or unsubstituted aryl group, camphor group, camphorquinone group, Any one of the naphthyl azide groups.

According to another aspect of the present invention, a method for preparing the aforementioned sulfonate photoacid generator is provided. The preparation method includes: step S1, reacting compound 1 with R ¹ ′Y to generate compound 2; step S1 S2, perform a hydroxylamination reaction on compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound; step S3, perform an esterification reaction on the hydroxylamine compound with R ² SO ₂ X ² or (R ² SO ₂ ) ₂ O to obtain sulfonic acid Ester photoacid generator; the structural formulas of Compound 1 and Compound 2 are as follows:

Among them, X ¹ is selected from any one of -H, -OH, -SH and halogen atoms, Y is selected from any one of -OH ^, -CH＝CH ₂ , -C≡CH and halogen atoms, is a halogen atom, R ¹ ′Y reacts with the X ¹ substituent in compound 1 to generate the R ¹ substituent. When Y is a halogen atom, R ¹ =R ¹ ′; when Y is OH, R ¹ =R ¹ ′ -O-, when Y is -CH=CH ₂ , R ¹ =R ^1' -CH=CH-, when Y is -C≡CH, R ¹ =R ^1' -C≡C-, R ¹ , R ² is the same as R ¹ and R ² mentioned above.

According to another aspect of the present invention, a resist composition is provided, including a resin component and an acid generator, and the acid generator is the above-mentioned sulfonate photoacid generator.

According to yet another aspect of the present invention, a patterning method is provided, which includes mixing, film forming and patterning processing of a resist composition, which is the aforementioned resist composition.

According to another aspect of the present invention, an application of the aforementioned resist composition is provided, which application includes applying the resist composition to the preparation of protective films, interlayer insulating materials, and pattern transfer materials for electronic components. middle.

Applying the technical solution of the present invention, the molecule of the sulfonate photoacid generator with general formula I in this application contains a sulfonate group, and the sulfonate group is directly connected to the imide structure, and the structure has photosensitive cleavage Characteristics: N-O bonds can be broken under active energy ray irradiation to produce different types of sulfonic acids. The above-mentioned active energy rays are active energy rays with wavelengths between 300 and 450nm in the near-ultraviolet and visible light regions. In particular, they have high sensitivity and strong absorption for active energy rays with a wavelength of 365nm (i-line), which will include the sulfonate. When the resist composition of the acid ester photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkali developer, due to the improvement in sensitivity of the sulfonate photoacid generator, it can form a film with excellent Sensitivity and good contrast patterns, even when forming fine patterns, can have sufficiently high resolution and sensitivity. At the same time, the substituent of the sulfonate photoacid generator of the present invention contains an epoxy group structure, which can open the ring under acidic and high-temperature conditions, but does not open the ring under neutral and high-temperature conditions, thereby helping to reduce The dosage of additives in the resist reduces the diffusion of photoacid molecules and improves the firmness of the photolithography pattern.

Detailed ways

It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of this application can be combined with each other. The present invention will be described in detail below with reference to examples.

As analyzed in the background art, there are problems in the prior art such as acid migration and poor photolithographic pattern fastness. In order to solve this problem, the present invention provides a sulfonate photoacid generator and its preparation method and pattern. Chemical methods, resist compositions and their applications.

In a typical embodiment of the present application, a sulfonate ester photoacid generator is provided. The sulfonate ester photoacid generator has the following general formula (I):

Wherein, R ¹ is selected from a substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group, a substituted or unsubstituted C ₂ to C ₂₅ alkoxy group, a substituted or unsubstituted C ₂ to C ₂₅ alkylthio group. Any one, in which -CH ₂ - can be optionally replaced by -O-, -S-, -CO-, -O-CO- or -COO-, and the C atom can also be optionally replaced by N atom Substituted, and the terminal of the substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group, the substituted or unsubstituted C ₂ to C ₂₅ alkoxy group, the substituted or unsubstituted C ₂ to C ₂₅ alkylthio group contains at least A substituted or unsubstituted C ₂ to C ₁₀ epoxy group; R ² is selected from a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₁₈ substituted or unsubstituted aryl group, camphor group, camphorquinone group, Any one of the naphthyl azide groups.

The sulfonate photoacid generator with the general formula I in this application contains a sulfonate group in its molecule. The sulfonate group is directly connected to the imide structure. This structure has photosensitive cleavage characteristics and can be activated when irradiated with active energy rays. N-O bond cleavage can occur under the conditions to produce different types of sulfonic acids. The above-mentioned active energy rays are active energy rays with wavelengths between 300 and 450nm in the near-ultraviolet and visible light regions. In particular, they have high sensitivity and strong absorption for active energy rays with a wavelength of 365nm (i-line), which will include the sulfonate. When the resist composition of the acid ester photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkali developer, due to the improvement in sensitivity of the sulfonate photoacid generator, it can form a film with excellent Sensitivity and good contrast patterns, even when forming fine patterns, can have sufficiently high resolution and sensitivity. At the same time, the substituent of the sulfonate photoacid generator of the present invention contains an epoxy group structure, which can open the ring under acidic and high-temperature conditions, but does not open the ring under neutral and high-temperature conditions, thereby helping to reduce The dosage of additives in the resist reduces the diffusion of photoacid molecules and improves the firmness of the photolithography pattern.

In one embodiment of the present application, the substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group is selected from the group consisting of substituted or unsubstituted C ₂ to C ₂₅ linear alkyl group, substituted or unsubstituted C ₃ to C ₂₅ Any one of branched alkyl groups, substituted or unsubstituted C ₄ to C ₂₅ alkenyl groups, substituted or unsubstituted C ₄ to C ₂₅ alkynyl groups; preferably R ¹ is selected from substituted or unsubstituted C ₆ to C ₁₇ branched alkyl group, substituted or unsubstituted C ₉ to C ₁₆ alkenyl group, substituted or unsubstituted C ₉ to C ₁₈ alkynyl group, substituted or unsubstituted C ₆ to C ₁₇ alkyl group Any one of an oxygen group and a substituted or unsubstituted C ₆ to C ₁₅ alkylthio group;

Further, preferably the substituted or unsubstituted C ₆ to C ₁₇ branched alkyl group is selected from Any one of them; preferably the substituted or unsubstituted C ₉ to C ₁₆ alkenyl group is selected from Any one of them; preferably the substituted or unsubstituted C ₉ to C ₁₈ alkynyl group is selected from Any one of them; preferably the substituted or unsubstituted C ₆ to C ₁₇ alkoxy group is selected from Any one of them; preferably the substituted or unsubstituted C ₆ to C ₁₅ alkylthio group is selected from Among them, "*" is the position where R ¹ is connected to the naphthalene ring of the sulfonate photoacid generator.

In order to make it easier to synthesize the above-mentioned sulfonate photoacid generator and take into account the cost, it is preferable that R ¹ is selected from a substituted or unsubstituted C ₉ to C ₁₆ alkenyl group, a substituted or unsubstituted C ₉ to C ₁₈ alkynyl group, Any one of substituted or unsubstituted C ₆ to C ₁₇ alkoxy groups; considering that the alkenyl group is prone to yellowing, for a transparent system, it is more preferred that R ¹ is selected from substituted or unsubstituted C ₉ to C ₁₈ alkyne group, any one of substituted or unsubstituted C ₆ to C ₁₇ alkoxy groups.

In one embodiment of the present application, the above-mentioned epoxy group is a C ₂ to C ₅ epoxy group, and preferably the epoxy group is selected from Any one of them, further preferably

The number of ring carbon atoms of the epoxy group will affect the difficulty of ring opening. The preferred epoxy group is more conducive to improving the ring opening of the sulfonate photoacid generator under acidic and high temperature conditions.

In order to further improve the structural stability and performance of the sulfonate photoacid generator, it is preferred that in the above-mentioned R ² , the C ₁ to C ₂₀ alkyl group is selected from substituted or unsubstituted C ₁ to C ₂₀ linear alkyl groups. , any one of substituted or unsubstituted C ₃ to C ₂₀ branched alkyl groups, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl groups; preferably R ² is selected from C ₁ to C ₁₀ alkyl groups , any one of a C ₆ to C ₁₀ substituted or unsubstituted aryl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, a camphor group, a camphorquinone group, or a naphthyl azide group; further , preferably R ² is selected from a substituted or unsubstituted C ₁ to C ₈ linear alkyl group, a substituted or unsubstituted C ₃ to C ₈ branched alkyl group, a substituted or unsubstituted C ₃ to C ₅ ring Any one of an alkyl group, a substituted or unsubstituted phenyl group, a camphor group, a camphorquinone group, or an azide group; further, it is preferred that the substituent in R ² is a halogen atom, and further, it is preferred that it is a fluorine atom ;Furthermore, it is preferred that R ² is selected from C ₁ to C ₄ linear perfluoroalkyl groups, C ₁ to C ₄ linear alkyl groups, C ₃ to C ₆ branched perfluoroalkyl groups, perfluoroalkyl groups, Any one of a fluorophenyl group, a C ₁ to C ₄ perfluoroalkyl substituted phenyl group, a C ₁ to C ₄ alkyl substituted phenyl group, a camphor group, a camphorquinone group, or a naphthyl azide group. species; preferably R ² is selected from any one of trifluoromethyl, perfluorobutyl, n-propyl, n-butyl, camphor, p-tolyl, and o-trifluoromethylphenyl.

In some embodiments of the present application, it is preferred that the structural formula of the above-mentioned sulfonate photoacid generator is selected from the group consisting of:



any one or more of them, thereby further improving the photoinduced

Excellent performance of resist.

In another typical embodiment of the present application, a method for preparing the aforementioned sulfonate ester photoacid generator is provided. The preparation method includes: step S1, reacting compound 1 with R ¹ ′Y, Generate compound 2; step S2, perform a hydroxylamination reaction on compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound; step S3, esterify the hydroxylamine compound with R ² SO ₂ X ² or (R ² SO ₂ ) ₂ O Reaction to obtain a sulfonate photoacid generator; the structural formulas of Compound 1 and Compound 2 are as follows:

Among them, X ¹ is selected from any one of -H, -OH, -SH and halogen atoms, Y is selected from any one of -OH ^, -CH＝CH ₂ , -C≡CH and halogen atoms, is a halogen atom, R ¹ ′Y reacts with the X ¹ substituent in compound 1 to generate the R ¹ substituent. When Y is a halogen atom, R ¹ =R ¹ ′; when Y is OH, R ¹ =R ¹ ′ -O-, when Y is -CH=CH ₂ , R ¹ =R ^1' -CH=CH-, when Y is -C≡CH, R ¹ =R ^1' -C≡C-, R ¹ , R ² is the same as R ¹ and R ² mentioned above.

In the above step S1, the 4-substituted naphthalene anhydride (compound 1) can be reacted with terminally substituted R ¹ 'Y (halogenated hydrocarbons, alkenes, alkynes, alcohols and other substances) through Friedel-Crafts reaction, Heck coupling reaction, addition Different types of reactions such as formation reaction or Click reaction are used to obtain the naphthalene anhydride (compound 2) substituted by R ¹ at the 4-position, in which R ¹ ′Y can be purchased, or can be obtained through primary alcohol, carboxylic acid, terminal alkene, terminal olefin, etc. It is prepared by esterification, etherification and addition reactions between alkynes and halogenated hydrocarbons. In step S2, the naphthalene anhydride substituted with ^R1 at the 4-position undergoes a hydroxylamination reaction with a hydroxylaminating reagent under alkaline or acidic conditions to generate a hydroxylamine compound, wherein the hydroxylaminating reagent can be hydroxylamine sulfate or hydroxylamine hydrochloride, preferably hydroxylamine. The reaction temperature is controlled between 25 and 100°C, and more preferably between 75 and 100°C, which is more conducive to improving the efficiency of the hydroxylamination reaction. In step S3, an esterification reaction occurs between the hydroxylamine compound and the acylating reagent in an inert solvent under alkaline conditions to generate a sulfonate ester compound. The temperature of the esterification reaction is preferably controlled between -10°C and 60°C, and more preferably between 0°C and 25°C, which is more conducive to improving the efficiency of the esterification reaction.

In addition, the raw materials and reagents used in the above preparation method are all known compounds in the prior art, and can be obtained commercially or conveniently prepared through known processes, and will not be described again here.

The sulfonate ester photoacid generator of the present invention can be used for any known uses of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, and resists for MEMS. , materials for stereolithography and micro-stereolithography, etc. Among them, as the photoacid generator in the resist composition, the resist can be prepared together with the resin having an acid-dissociating group and used in semiconductor photolithography.

In another typical embodiment of the present application, a resist composition is provided, including a resin component and an acid generator, and the acid generator is the aforementioned sulfonate photoacid generator.

The resist composition of the present invention can be divided into positive-type compositions and negative-type compositions according to applications. In addition to the sulfonate photoacid generator, the positive composition generally contains a resin component (B1) that increases the solubility in an alkali developer through the action of an acid. During the composition pattern formation process, through selective exposure, the acid-labile groups protected by protective groups in the positive resin in the exposed area will be deprotected by the acid generated by the photoacid generator, making them Soluble in alkali developer. Therefore, when alkali development is performed, the pattern in the unexposed area remains, forming a positive pattern. Unlike the positive composition, the negative composition uses a resin-crosslinking agent component (B2) that is cross-linked by the action of an acid and is insoluble in an organic developer. The exposed area is catalyzed by the acid generated by the photoacid generator, and the resin reacts with the cross-linking agent to form a polymer that is insoluble in the organic developer and remains, while the unexposed area is dissolved and removed by the organic developer, and finally forms a negative type Figure, among which, for the specific resin component (B1) and resin-crosslinking agent component (B2), please refer to the specific content disclosed in paragraphs [0046] to [0076] of the Chinese patent application with application number 202011299973.1, here No longer.

In the positive/negative resist composition of the present invention, the sulfonate photoacid generator can break the N-O bond to generate sulfonic acid under the irradiation of active energy rays. Through the PEB process, the exposed area and the unexposed area can be aligned. Differences in developer solubility. The sulfonate photoacid generator product can be used alone or in a mixture of two or more.

Benefiting from the performance of the sulfonate ester photoacid generator with general formula I in the present application, the resist composition including the sulfonate ester photoacid generator and the resin component is used for dissolution exposure with an alkali developer. When using a photosensitive composition, even fine patterns can be formed with sufficiently high resolution and sensitivity. At the same time, the amount of additives in the resist can be reduced, the diffusion of photoacid molecules can be reduced, and the firmness of the photolithographic pattern can be improved.

In one embodiment of the present application, the above-mentioned resin component has an acid-labile group protected by a protecting group, and the acid-labile group is selected from at least one of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group; preferably The content of the acid-labile group accounts for 1 to 80% of the resin component content, preferably 3 to 70%; the preferred protecting group includes at least one of the groups represented by formula (a) and formula (b):

Wherein, in formula (a), R ³ is selected from a substituted or unsubstituted C ₁ to C ₂₀ linear alkyl group, a substituted or unsubstituted C ₃ to C ₂₀ branched alkyl group, a substituted or unsubstituted C Any one or more of ₃ to C ₂₀ cycloalkyl groups, preferably R ³ is selected from substituted or unsubstituted C ₁ to C ₁₀ straight chain alkyl groups, substituted or unsubstituted C ₃ to C ₁₀ branched alkyl groups. Any one or more of an alkyl group and a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group. Furthermore, preferably R ³ is selected from a substituted or unsubstituted C ₁ to C ₆ linear alkyl group. , any one or more of substituted or unsubstituted C ₃ to C ₆ branched alkyl groups, substituted or unsubstituted C ₃ to C ₆ cycloalkyl groups, preferably the substitution described when R ³ has a substituent The group is selected from any one or more of halogen, hydroxyl, cyano, C ₁ to C ₄ linear alkyl, C ₃ to C ₅ branched alkyl, and the preferred substituent is selected from fluorine atom, methyl , any one or more of ethyl groups, preferably one or more C atoms in R ³ can be substituted by any heteroatom in O, S, N or Si; further, preferably R ³ is selected from methoxy group , ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxyethoxy, Any one or more of them, in formula (b), R ⁴ is selected from a substituted or unsubstituted C ₁ to C ₂₀ linear alkyl group, a substituted or unsubstituted C ₃ to C ₂₀ branched alkyl group , any one or more of substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl groups, and n is 0 or 1, preferably R ⁴ is selected from substituted or unsubstituted C ₁ to C ₁₀ linear alkyl groups group, any one or more of substituted or unsubstituted C ₃ to C ₁₀ branched alkyl groups, substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl groups, further, preferably R ⁴ is selected from substituted Or any one of unsubstituted C ₁ to C ₆ linear alkyl groups, substituted or unsubstituted C ₃ to C ₆ branched alkyl groups, and substituted or unsubstituted C ₃ to C ₆ cycloalkyl groups. or more; further, preferably R ⁴ is selected from any one or more of tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl, tert-butoxycarbonylmethyl.

Preferably, the resin component of the above type is beneficial to its synergistic effect with the sulfonate photoacid generator to obtain a strong photolithography pattern.

The dosage of the above-mentioned acid generator can refer to the dosage of conventional acid generators in the prior art. In one embodiment, the weight content of the acid generator is 0.5 to 5% relative to the mass of the solid content of the resist composition. , preferably 1 to 3%, so that good sensitivity can be exerted and the development effect can be improved.

The solvent is used to dissolve various components in the resist composition to form a uniform solution, and is used to adjust its viscosity and coating properties to facilitate film formation. For specific solvents, please refer to the Chinese patent application with application number 202011299973.1. Optionally, the resist composition may also contain conventional additives in this field, which will not be described again here.

In another typical embodiment of the present application, a patterning method is provided, including mixing, film forming and patterning processing of a resist composition, which is the above-mentioned resist combination. things.

When applying the resist composition of the present invention, first a resin solution dissolved or dispersed in an organic solvent can be applied on a substrate using, for example, spin coating, and then heated to volatilize the solvent, thereby forming a resist composition on the substrate. The film is etched, and then light irradiation (that is, exposure) in the shape of a wiring pattern is performed, and then a post-exposure heat treatment (PEB) is performed, followed by alkaline development to form a wiring pattern.

The drying conditions of the coated resin solution vary depending on the solvent used, but it is preferably carried out at 50 to 150°C and within the range of 1 to 30 minutes, that is, it is appropriately determined based on the amount of residual solvent (mass percentage) after drying, etc. .

After the resist film is formed on the substrate, the wiring pattern shape is irradiated with light. Light irradiation can use low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (such as argon lasers, dye lasers, Nitrogen laser, LED, helium cadmium laser), etc., preferably high-pressure mercury lamp and LED lamp.

The temperature of the post-exposure heat treatment (PEB) is usually 40 to 200°C, preferably 60 to 150°C. If it is less than 40°C, the deprotection reaction or the cross-linking reaction cannot fully proceed, so the difference in solubility between the exposed part and the unexposed part is insufficient to form a pattern. If it is higher than 200°C, there is a problem of reduced productivity. The above heating time is usually 0.5 to 30 minutes.

Develop with an alkali developer. The alkali development method includes the use of an alkali developer. The alkaline developer can be selected from aqueous solutions of 0.1 to 10% (mass percentage) tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate. The alkaline developer can also include water-soluble organic solvents, such as Methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N-methylpyrrolidone, etc. The development method can be selected from dipping method, spray method and spray method, with spray method being preferred. The temperature of the developer is preferably used at 25 to 40° C., the development time is appropriately determined according to the thickness of the resist film, and finally a pattern corresponding to the mask is obtained.

In another typical embodiment of the present application, an application of the above-mentioned resist composition is provided. The application includes applying the resist composition to protective films, interlayer insulating materials, and patterns of electronic components. Preparing transfer materials.

The above-mentioned applications can specifically include forming an interlayer insulating film from the resist composition for use in TFTs and panels of liquid crystal display devices; it can also be used as a protective film for color filters and spacers, and as PS photoresist and BCS photoresist. Resistor is used for pattern transfer.

The above-mentioned 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 and other electronic components.

The beneficial effects of the present application will be described below with reference to specific embodiments.

Preparation Example of Sulfonate Photoacid Generator

Example 1

Under nitrogen protection, in a 500mL four-necked flask, add 200g of toluene, 27.71g of 4-bromo-1,8-naphthalenedicarboxylic anhydride (S1), 3-ethyl-3-((2-(vinyl)ethyl) 20.49g of oxy)methyl)oxyalkyl, 0.22g of palladium acetate, 0.52g of triphenylphosphine, and 11.13g of triethylamine. Start stirring and raise the temperature to 75-80°C, and keep the reaction for 6 hours. Stop stirring, and after cooling to room temperature, add 100 mL of n-hexane, stir for 0.5 h, filter, rinse the filter cake once with 20 g of toluene, and combine the organic phases. Remove the solvent under reduced pressure, then dissolve the mixed system with 100g DCM, add 3g of activated carbon, stir and decolorize, and obtain 30.10g of intermediate T1-1 through column chromatography after removing the solvent.

In a 250 mL four-necked flask, add 100 g of water, 19.12 g of intermediate T1-1, 4.17 g of hydroxylamine hydrochloride, and 4.63 g of ammonium acetate. Start stirring and raise the temperature to 75-80°C, and keep the reaction for 3 hours. Stop stirring, cool slightly and then filter while hot. The filtered solids are rinsed with about 100g of pure water and dried to obtain 13.95g of intermediate T1-2, which is a light yellow solid.

Under nitrogen protection, add 200g of methylene chloride, 13.95g of intermediate T1-2, and 3.33g of pyridine into a 250mL four-necked flask. Stir evenly and then cool to 0~5°C. Slowly drop in 11.88% of trifluoromethanesulfonic anhydride. g, maintain the temperature and stir for 3 hours. Add 50g of pure water, stir for 0.5h, separate the liquids, concentrate the organic phase at 55°C under normal pressure until no distillation occurs, add 50g of n-hexane for crystallization, and obtain 15.25g of sulfonate photoacid generator 34, which is a light yellow solid. .

Example 2

In a 500mL four-necked flask, add 250g of tetrahydrofuran, 19.82g of 1,8-naphthalenedicarboxylic anhydride, 26.66g of aluminum trichloride, and 16.15g of 3-ethyl-3-(chloromethyl)-oxoalkane, and open Stir, stir evenly, then raise the temperature to 70°C and reflux for 12 hours. Stop stirring, cool the system to room temperature, remove the solvent in vacuo, add 100g of pure water and 150g of methylene chloride, shake well and separate the liquid. The organic phase was concentrated to obtain 15.56 g of intermediate T2-1 as a white solid.

For the preparation of T2-2 and photoacid 1, please refer to the second and third reactions in Example 1.

Example 3

The preparation method of the sulfonate photoacid generator 28 can be referred to Example 1.

Example 4

In a 250mL stainless steel pressure kettle, add 150g of methanol, 17.62g of intermediate T3-1, 0.15g of 5% Pd/C catalyst, and 0.5mL of acetic acid. After leak detection and sealing, fill in 1 to 2MPa of hydrogen and start stirring. And raise the temperature to 55~65℃, and keep the reaction for 6 hours. Stop stirring and allow to cool to room temperature. Filter, remove the solvent under reduced pressure, then dissolve the mixed system with 100g of DCM, add 3g of activated carbon, stir and decolorize, remove the solvent and obtain 16.35g of intermediate T4-1 as a white solid through column chromatography.

For the preparation of T4-2 and sulfonate photoacid generator 8, please refer to the second and third reactions in Example 1.

Example 5

Under nitrogen protection, in a 500mL four-necked flask, add 200g of 3-ethyl-3-oxetanemethanol, 27.71g of 4-bromonaphthalic anhydride, 41.46g of potassium carbonate, and 0.67g of anhydrous copper chloride. Raise the temperature, reflux and stir for 12 hours, then stop heating. After returning to room temperature, filter, add 500g of n-hexane to the filtrate, stir and crystallize at 0°C for 0.5h. Filter, collect the filter cake, and rinse with 20 mL n-hexane. Dissolve the filter cake with a small amount of DCM, filter and purify by column chromatography, and finally obtain 21.55g of intermediate T5-1 as a white solid.

For the preparation of T5-2 and sulfonate photoacid generator 15, please refer to the second and third reactions in Example 1.

Example 6

Under nitrogen protection, add 20g of 3-ethyl-3-oxetanemethanol and 200mL of THF into a 500mL four-necked flask, stir evenly and then cool to 0°C. Add a total of 4.80g of NaH in batches and control the reaction temperature below 5°C. After stirring evenly, maintain the temperature at 0°C, slowly add 17.07g of bromopropyne into the reactor, and after the addition is completed, slowly rise to room temperature and react for 3 hours. The reaction was stopped, the reaction solution was filtered and concentrated, and purified by column chromatography to obtain 15.20 g of 3-ethyl-3-oxetane propargyl ether.

Under nitrogen protection, in a 500mL four-necked flask, add 18.50g of 3-ethyl-3-oxetane propargyl ether, 27.71g of 4-bromonaphthalic anhydride, and 300mL of THF. Stir evenly and then add methylene iodide. Copper 0.95g, triphenylphosphine 2.62g, bistriphenylphosphine palladium dichloride 0.70g, triethylamine 20.24g, raise to 70°C and stir for 3 hours, stop heating. After returning to room temperature, the solvent was concentrated to remove, and purified by column chromatography to finally obtain 29.78 g of intermediate T6-1 as a light yellow solid.

For the preparation of T6-2 and sulfonate photoacid generator 35, please refer to the second and third reactions in Example 1.

Example 7

For the preparation of T6-1 and T6-2, please refer to Example 6.

In a 500mL four-necked flask, add 18.27g T6-2 and 200mL dichloromethane, stir and dissolve, add 7.59g triethylamine, and cool to 0°C for 15 minutes. Add a total of 10.49g of p-toluenesulfonyl chloride in batches into the reactor, and control the system temperature not to exceed 5℃. After the stirring reaction for 3 hours, slowly add 100 mL of ammonia water into the system, and separate the liquids after the system is stable. The organic phase was washed with 50 mL of 0.5 M hydrochloric acid, and then washed twice with 100 mL of pure water each time. Concentrate the organic phase until solid precipitates, add 200 mL of n-hexane, stir and crystallize. After filtration and drying, 20.00g of light yellow solid was obtained, which was sulfonate photoacid generator 50.

Example 8

For the preparation of T6-1 and T6-2, please refer to Example 6. For the preparation of the sulfonate photoacid generator 52, refer to Example 7, and replace the p-toluenesulfonyl chloride raw material with butanesulfonyl chloride.

Referring to the reaction steps similar to Examples 1 to 8, Examples 9 to 21 respectively replaced the substrates and adjusted the reaction conditions accordingly to obtain other corresponding sulfonate ester photoacid generators 2, 11, 13, 14, 18, and 21. ,24,25,27,29,32,36,39.

Example 22

For the preparation of the sulfonate photoacid generator 49, refer to Example 7, and replace the raw material of p-toluenesulfonyl chloride with suspended camphorsulfonyl chloride.

Example 23

For the preparation of the sulfonate photoacid generator 51, refer to Example 7, and replace the raw material of p-toluenesulfonyl chloride with propanesulfonyl chloride.

Example 24

For the preparation of the sulfonate photoacid generator 53, refer to Example 7, and replace the p-toluenesulfonyl chloride raw material with 2-trifluoromethylbenzenesulfonyl chloride.

The numbers and 1HNMR characterization results of the sulfonate photoacid generators prepared in all examples are listed in Table 1 respectively.

Table 1

Performance evaluation

The performance of the sulfonate ester photoacid generator synthesized in Examples 1 to 24 and the sulfonate ester photoacid generator synthesized in Comparative Example 1 was evaluated respectively. The evaluation indicators include molar absorption coefficient, solubility and chemical stability.

(1)Molar absorption coefficient

The compound was diluted to 0.25 mmol/L with acetonitrile, and the absorbance of a cuvette length of 1 cm was measured in the range of 200 to 600 nm using a UV-visible spectrophotometer (UPG-752). The molar absorption coefficient ε at each wavelength is calculated according to the following formula, that is, ε (L·mol ^-1 ·cm ^-1 )=A/(0.00025mol/L×1cm), where A represents the absorbance at each wavelength.

(2)Solubility

High solubility not only makes the photoacid generator compound easy to purify, but also enables the photoacid generator compound to expand the concentration range of use in photoresists and different solvent systems. Take 1.0000g of the photoacid generator compound product respectively, and gradually add the solvent at 25°C until all the solids in each test tube are completely dissolved. Record the mass of the solvent used. Solubility = (1g/solvent mass) × 100%. The evaluation results are as shown in Table 2. shown in .

Table 2

The nonionic photoacid generator of Comparative Example 1 is Record it as A*1.

It can be seen from the test results in Table 2 that the photoacid generator of the present invention has a high molar absorption coefficient at 365nm, has strong light absorption ability, can fully utilize light energy, and can ensure a high utilization rate in resist applications. , and showed good solubility.

Examples of Resist Compositions

Referring to the formulas shown in Resist Composition Examples 1 to 31 and Resist Composition Comparative Examples 1 to 6 in Table 3, uniformly dissolve each raw material in PGMEA (propylene glycol methyl ether acetate) to obtain the solid content concentration. Approximately 20% (mass percent) of the resist composition. Among them, the component types and contents of the sulfonate photoacid generator (A), resin component (B), and acid binding agent triethylamine (C) are as shown in Table 3.

Composition Example 1

The resin component (B) adopts type B ₁ resin and is composed of repeating units represented by formula B ₁₁ , formula B ₁₂ and formula B ₁₃ . The numerical value at the lower right of each repeating unit represents the content (mass) of the repeating unit in the resin. percentage). The weight average molecular weight of B ₁ resin is approximately 10,000.

The sulfonate ester photoacid generator (A) is the sulfonate ester photoacid generator of Example 1.

Composition Examples 2 to 24

The difference from Composition Example 1 is that: the sulfonate ester photoacid generator (A) adopts the sulfonate ester photoacid generators of Examples 2 to 24 in sequence.

The remaining component types and contents are shown in Table 3.

Composition Example 25

The difference from Composition Example 5 is that the resin component (B) adopts _B2 type resin, which is composed of repeating units represented by formula _B21 , formula _B22 and formula _B23 . The numerical value on the lower right of each repeating unit indicates The content (mass %) of this repeating unit in the resin. The weight average molecular weight of _B2 resin is approximately 10,000.

Composition Example 26

The difference from Composition Example 5 is that the resin component (B) adopts _B3 type resin and is composed of repeating units represented by formula _B31 and formula _B32 . The numerical value on the lower right of each repeating unit indicates that the repeating unit is in Content in resin (mass %). The weight average molecular weight of _B3 resin is approximately 10,000.

Composition Examples 27-28

The difference from Composition Example 5 is that the content of the sulfonate photoacid generator is different.

Composition Example 29

The difference from Composition Example 5 is that no acid binding agent is added.

Composition Example 30

The difference from Composition Example 6 is that no acid binding agent is added.

Composition Example 31

The difference from Composition Example 7 is that no acid binding agent is added.

Composition Comparative Example 1

The difference from Composition Example 5 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used.

Composition Comparative Example 2

The difference from Composition Example 6 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used.

Composition Comparative Example 3

The difference from Composition Example 7 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used.

Composition Comparative Example 4

The difference from Composition Comparative Example 1 is that no acid binding agent is added.

Composition Comparative Example 5

The difference from Composition Comparative Example 2 is that no acid binding agent is added.

Composition Comparative Example 6

The difference from composition comparative example 3 is that no acid binding agent is added.

The resist compositions prepared in Composition Examples 1 to 31 and Composition Comparative Examples 1 to 6 were evaluated for sensitivity and resolution by the following methods, and the results are recorded in Table 3.

(1) Sensitivity evaluation

On each silicon wafer, the resist composition of each Example and Comparative Example was coated with a film thickness of 1 μm capable of forming a pattern to form a coating film. The formed coating film was pre-baked at 90°C for 100 seconds. After prebaking, the coating film was exposed through a hole pattern forming mask with a diameter of 10 μm while gradually changing the exposure amount (exposure wavelength: 365 nm), and then developed with a 2.0% tetramethylammonium hydroxide aqueous solution at 25°C for 30 seconds. . The minimum exposure required to form a 10 μm diameter hole pattern was determined by the above method. From the minimum exposure value obtained, the sensitivity was evaluated according to the following criteria: "○" indicates a sensitivity of -50mJ/ ^cm2 or less, and "×" indicates a sensitivity of -300mJ/cm2 ^or more.

(2)Resolution evaluation

Using a mask for forming a hole pattern with a diameter of 5 μm, coating film formation, coating film exposure, and development were performed in the same manner as for sensitivity evaluation, except for exposure at ^an exposure dose of 100 mJ/cm. The developed coating film was observed, and the resolution was evaluated according to the following criteria: "○" indicates that a pattern with a diameter of 5 μm can be formed, and "○" indicates that a pattern with a diameter of 5 μm cannot be formed.

table 3

It can be seen from the results in Table 3 that the resist compositions of the present invention as shown in Composition Examples 1 to 28 have very good sensitivity and resolution, which are significantly better than those of Comparative Examples 1 to 3. Composition Examples 29 to 31 show that in the absence of acid binding agent In this case, the resolution is still very good, but the compositions Comparative Examples 4 to 6, which also do not add an acid binding agent, show average resolution.

From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects:

The sulfonate photoacid generator with the general formula I in this application contains a sulfonate group in its molecule. The sulfonate group is directly connected to the imide structure. This structure has photosensitive cleavage characteristics and can be activated when irradiated with active energy rays. N-O bond cleavage can occur under the conditions to produce different types of sulfonic acids. The above-mentioned active energy rays are active energy rays with wavelengths between 300 and 450nm in the near-ultraviolet and visible light regions. In particular, they have high sensitivity and strong absorption for active energy rays with a wavelength of 365nm (i-line), which will include the sulfonate. When the resist composition of the acid ester photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkali developer, due to the improvement in sensitivity of the sulfonate photoacid generator, it can form a film with excellent Sensitivity and good contrast patterns, even when forming fine patterns, can have sufficiently high resolution and sensitivity. At the same time, the substituent of the sulfonate photoacid generator of the present invention contains an epoxy group structure, which can open the ring under acidic and high-temperature conditions, but does not open the ring under neutral and high-temperature conditions, thereby helping to reduce The dosage of additives in the resist reduces the diffusion of photoacid molecules and improves the firmness of the photolithography pattern.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (11)

1. A sulfonate ester photoacid generator, characterized in that the sulfonate ester photoacid generator has the following general formula (I):
   

   Wherein, R ¹ is selected from a substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group, a substituted or unsubstituted C ₂ to C ₂₅ alkoxy group, a substituted or unsubstituted C ₂ to C ₂₅ alkylthio group. Any one, in which -CH ₂ - can be optionally replaced by -O-, -S-, -CO-, -O-CO- or -COO-, and the C atom can also be optionally replaced by N atom Substituted, and the substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group, the substituted or unsubstituted C ₂ to C ₂₅ alkoxy group, the substituted or unsubstituted C ₂ to C ₂₅ alkylthio group The terminal end of the group contains at least one substituted or unsubstituted C ₂ to C ₁₀ epoxy group;

   R ² is selected from any one of a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₁₈ substituted or unsubstituted aryl group, a camphor group, a camphorquinone group, or a naphthyl azide group.
2. The sulfonate photoacid generator according to claim 1, wherein the substituted or unsubstituted C ₂ to C ₂₅ hydrocarbon group is selected from the group consisting of substituted or unsubstituted C ₂ to C ₂₅ linear alkane. Any one of the group, a substituted or unsubstituted branched chain alkyl group of C ₃ to C ₂₅ , a substituted or unsubstituted alkenyl group of C ₄ to C ₂₅ , or a substituted or unsubstituted alkynyl group of C ₄ to C ₂₅ ;

   Preferably, R ¹ is selected from substituted or unsubstituted C ₆ to C ₁₇ branched alkyl groups, substituted or unsubstituted C ₉ to C ₁₆ alkenyl groups, and substituted or unsubstituted C ₉ to C ₁₈ alkynyl groups. , any one of a substituted or unsubstituted C ₆ to C ₁₇ alkoxy group, a substituted or unsubstituted C ₆ to C ₁₅ alkylthio group;

   Further, it is preferred that the substituted or unsubstituted C ₆ to C ₁₇ branched alkyl group is selected from any of;

   Preferably, the substituted or unsubstituted C ₉ to C ₁₆ alkenyl group is selected from any of;

   Preferably, the substituted or unsubstituted C ₉ to C ₁₈ alkynyl group is selected from any of;

   Preferably, the substituted or unsubstituted C ₆ to C ₁₇ alkoxy group is selected from any of;

   Preferably, the substituted or unsubstituted C ₆ to C ₁₅ alkylthio group is selected from the group consisting of Among them, "*" means that R ¹ and the sulfonate esters photoacid-generate The position where the naphthalene ring of the agent is attached.
3. The sulfonate photoacid generator according to claim 1, wherein the epoxy group is a C ₂ to C ₅ epoxy group, preferably the epoxy group is selected from Any one of them, further preferably
4. The sulfonate photoacid generator according to any one of claims 1 to 3, characterized in that in the R ² , the C ₁ to C ₂₀ alkyl group is selected from substituted or unsubstituted C Any one of _{a 1} to C ₂₀ linear alkyl group, a substituted or unsubstituted C ₃ to C ₂₀ branched alkyl group, or a substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group;

   Preferably, R ² is selected from a C ₁ to C ₁₀ alkyl group, a C ₆ to C ₁₀ substituted or unsubstituted aryl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, camphor group, and camphorquinone. Any one of base and naphthalene azide base;

   Further, it is preferred that R ² is selected from substituted or unsubstituted C ₁ to C ₈ linear alkyl groups, substituted or unsubstituted C ₃ to C ₈ branched alkyl groups, substituted or unsubstituted C ₃ to C 8 alkyl groups. Any one of C ₅ cycloalkyl group, substituted or unsubstituted phenyl group, camphor group, camphorquinone group, and naphthalene azide group;

   Further, it is preferred that the substituent in R ² is a halogen atom, further, it is preferred to be a fluorine atom; further, it is preferred that R ² is selected from C ₁ to C ₄ linear perfluoroalkyl, C ₁ to C ₄ linear alkyl group, C ₃ to C ₆ branched perfluoroalkyl group, perfluorophenyl group, C ₁ to C ₄ perfluoroalkyl substituted phenyl group, C ₁ to C Any one of ₄ alkyl-substituted phenyl, camphor, camphorquinone, and naphthyl azide; preferably, R ² is selected from trifluoromethyl, perfluorobutyl, n-propyl, n-butyl Any one of base, camphor base, p-tolyl group and o-trifluoromethylphenyl group.
5. The sulfonate photoacid generator according to any one of claims 1 to 3, characterized in that the structural formula of the sulfonate photoacid generator is selected from the group consisting of:

   any one or more of them.
6. A method for preparing the sulfonate photoacid generator according to any one of claims 1 to 5, characterized in that the preparation method includes:

   Step S1, react compound 1 with R ¹ ′Y to generate compound 2;

   Step S2, performing a hydroxylamination reaction on the compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound;

   Step S3, perform an esterification reaction between the hydroxylamine compound and R ² SO ₂ X ² or (R ² SO ₂ ) ₂ O to obtain the sulfonate photoacid generator;

   The structural formulas of Compound 1 and Compound 2 are as follows:
   

   Among them, X ¹ is selected from any one of -H, -OH, -SH, and halogen atoms, and Y is selected from -OH, -CH=CH ₂ , -C ≡Any one of CH and halogen atoms, X ² is a halogen atom, R ¹ ′Y reacts with the X ¹ substituent in compound 1 to generate an R ¹ substituent, when Y is a halogen atom, R ¹ =R ¹ ′ , when Y is OH, R ¹ =R ¹ ′-O-, when Y is -CH=CH ₂ , R ¹ =R ^1' -CH=CH-, when Y is -C≡CH, R ¹ =R ^1' -C≡C-, R ¹ and R ² are the same as R ¹ and R ² according to any one of claims 1 to 5.
7. A resist composition includes a resin component and an acid generator, characterized in that the acid generator is the sulfonate photoacid generator according to any one of claims 1 to 5.
8. The resist composition according to claim 7, wherein the resin component has an acid-labile group protected by a protecting group, and the acid-labile group is selected from the group consisting of carboxyl groups, phenolic hydroxyl groups, At least one of the sulfonic acid groups; preferably, the content of the acid-labile group accounts for 1 to 80% of the content of the resin component, preferably 3 to 70%;

   Preferably, the protecting group includes at least one of the groups represented by formula (a) and formula (b):
   

   Wherein, in the formula (a), R ³ is selected from substituted or unsubstituted C ₁ to C ₂₀ linear alkyl, substituted or unsubstituted C ₃ to C ₂₀ branched alkyl, substituted or unsubstituted Any one or more C ₃ to C ₂₀ cycloalkyl groups, preferably R ³ is selected from substituted or unsubstituted C ₁ to C ₁₀ linear alkyl groups, substituted or unsubstituted C ₃ to Any one or more of C ₁₀ branched alkyl, substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl, further, preferably, R ³ is selected from substituted or unsubstituted C ₁ to C Any one or more of ₆ linear alkyl groups, substituted or unsubstituted C ₃ to C ₆ branched alkyl groups, substituted or unsubstituted C ₃ to C ₆ cycloalkyl groups, preferably the R When ³ has a substituent, the substituent is selected from any one or more of halogen, hydroxyl, cyano, C ₁ to C ₄ linear alkyl, C ₃ to C ₅ branched alkyl, preferably all The substituent is selected from any one or more of fluorine atoms, methyl, and ethyl. Preferably, one or more C atoms in R ³ can be substituted by any heteroatom in O, S, N, or Si. ; Further, it is preferred that R ³ is selected from methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1- Ethoxyethoxy, any one or more of,

   In the formula (b), R ⁴ is selected from substituted or unsubstituted C ₁ to C ₂₀ linear alkyl, substituted or unsubstituted C ₃ to C ₂₀ branched alkyl, substituted or unsubstituted C Any one or more of ₃ to C ₂₀ cycloalkyl groups, and n is 0 or 1. Preferably, R ⁴ is selected from substituted or unsubstituted C ₁ to C ₁₀ linear alkyl groups, substituted or unsubstituted Any one or more of substituted C ₃ to C ₁₀ branched alkyl groups, substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl groups, further, preferably, R ⁴ is selected from substituted or unsubstituted Any one or more of C ₁ to C ₆ linear alkyl groups, substituted or unsubstituted C ₃ to C ₆ branched alkyl groups, and substituted or unsubstituted C ₃ to C ₆ cycloalkyl groups. ; Further, it is preferred that R ⁴ is selected from any one or more of tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl, and tert-butoxycarbonylmethyl.
9. The resist composition according to claim 7 or 8, characterized in that the weight content of the acid generator is 0.01 to 5%, preferably 0.01 to 5%, relative to the mass of the solid content of the resist composition. 0.1 to 3%. Preferably, the resist composition further includes a solvent.
10. A patterning method, including mixing, film forming and patterning processing of a resist composition, characterized in that the resist composition is the resist combination according to any one of claims 7 to 9 things.
11. An application of the resist composition according to any one of claims 7 to 9, which application includes applying the resist composition to protective films, interlayer insulating materials, and pattern transfer of electronic components. Materials are being prepared.